Image forming process, image-recorded article, liquid composition and ink-jet recording apparatus

ABSTRACT

Disclosed herein is an image forming process for forming an image-recorded article having a coating layer on at least a part of an image formed, which comprises the steps of providing a liquid composition containing a polymer, providing an image-recorded article formed on a recording medium by an ink-jet recording method, and applying the liquid composition to at least a part of an image of the recorded article to insolubilize the polymer contained in the liquid composition on the surface of the image, thereby forming the coating layer at a position to which the liquid composition has been applied, wherein the recording medium has a surface which insolubilizes the polymer.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to an ink-jet recording process andan image-recorded article, and a liquid composition and an ink-jetrecording apparatus used in the formation thereof.

[0003] 2. Related Background Art

[0004] An ink-jet recording system is a system that minute droplets ofan ink are ejected by any of various kinds of operation principles toapply them to a recording medium such as paper, thereby recordingimages, characters, etc., and has been rapidly spread in variousapplication fields including information instruments as recordingapparatus of various images in recent years because of possiblehigh-speed recording, slight noise, easy color recording, highflexibility of recording patterns, needlessness of development andfixing, and the like. In addition, an image formed by a multi-colorink-jet system is about to be widely applied to a field of recordingfull-color images because recording comparable with multi-color printingof a plate system and prints by a color photography system can beprovided, and such an image is cheaper than those by the ordinarymulti-color printing and color photography system when the number ofcopies is small.

[0005] On the other hand, recoding media having a coating layer using analumina hydrate of a boehmite structure have been proposed. A typicalexample thereof is described in, for example, Japanese PatentApplication Laid-Open No. H7-232475.

[0006] These recording media using the alumina hydrate have such meritsthat fixing of a dye in an ink is good to provide an image having goodcoloring, and such recording medium are preferred to the conventionalrecording media from the viewpoints of image quality of a resultingimage, particularly, image quality of a full-color image, and glossbecause the alumina hydrate has a positive charge.

[0007] Under the circumstances, however, an image obtained by using suchdye ink and recording medium using the alumina hydrate described abovemay not have satisfactory performance as to resistance (gas resistance)to deterioration by a substance such as ozone gas in air in particularfrom the viewpoint of retaining the image quality of a high-qualityimage formed for a long period of time though it has image qualitycomparable with or superior to a silver salt print.

[0008] As a technique intended to improve the image durability of aresulting recorded article, it is disclosed to provide a protectivelayer on the surface of a recording medium after the formation of animage. For example, Japanese Patent Application Laid-Open No.2001-158092 discloses a process for laminating various kinds of plasticfilms as a protective film on an image-recorded article.

[0009] Japanese Patent Application Laid-Open No. H10-315448 describes aprocess in which fine particles composed of a thermoplastic polymer arecontained in an ink-receiving layer of a recording medium in advance,printing is performed in such a state that the ink absorbency is kept,and the fine particles are then melted or dissolved by heat or a solventto form a resin film as a protective film on the surface of therecording medium.

[0010] Japanese Patent Application Laid-Open No. 2000-225695, as anexample where the same system as an image forming method is used as ameans for forming a coating layer, discloses a method for forming acoating layer by ejecting an auxiliary liquid containing a resin havinga film-forming function, such as an emulsion, by an ink-jet system.Japanese Patent Application Laid-Open No. 2002-254796 describes thatovercoating or undercoating is applied with a treatment solutioncontaining an imidated styrene-maleic anhydride polymer by an ink-jetsystem.

SUMMARY OF THE INVENTION

[0011] However, the processes disclosed in Japanese Patent ApplicationLaid-Open No. H10-315448 and the like require to separately provide alaminator or an apparatus for melting or dissolving the fine particlescomposed of the thermoplastic polymer in addition to an image formingapparatus though the gas resistance is surely improved, and involve suchproblems that running cost is increased, and the whole apparatus islarge-scaled.

[0012] On the other hand, when such a resin having self-film-coatingproperty like emulsion as described in Japanese Patent ApplicationLaid-Open No. 2000-225695 is contained in the liquid for ejection,solidification (clogging at an orifice) may be easy to be caused byleaving it to stand for a long period of time at a minute orifice.

[0013] When the treatment solution is applied after penetration of anink into a recording medium in a system that the ink is reacted with thetreatment solution as described in Japanese Patent Application Laid-OpenNo. 2002-254796, no film is formed on the surface of the recordingmedium because the ink penetrated into the recording medium reacts withthe polymer, so that sufficient fastness properties for image may not beachieved in some cases. When the treatment solution is applied beforethe penetration of the ink into the recording medium, mist is generated,so that clogging at an orifice may be caused by reaction of the mist ofthe treatment solution with the ink in some cases.

[0014] The present invention has been made with a view toward solvingthe above-described problems and has as an object the provision of aprocess for forming an image-recorded article, by which animage-recorded article excellent in image quality, gas resistance andrub-off resistance can be provided by forming a coating layer on atleast a part of an image to be formed, occurrence of clogging at anorifice in an ink-jet recording apparatus due to use of a liquid forforming the coating layer can be prevented, and an image-recordedarticle excellent in image quality, gas resistance and rub-offresistance can be formed by forming a coating layer even by aminiaturized apparatus.

[0015] Another object of the present invention is to provide animage-recorded article excellent in image quality, gas resistance andrub-off resistance.

[0016] A further object of the present invention is to provide a liquidcomposition for forming a coating layer used in the process for formingan image-recorded article, and a recording apparatus using it.

[0017] The above objects can be achieved by the present inventiondescribed below.

[0018] According to the present invention, there is thus provided animage forming process for forming an image-recorded article having acoating layer on at least a part of an image formed, which comprises thesteps of

[0019] providing a liquid composition containing a polymer,

[0020] providing an image-recorded article formed on a recording mediumby an ink-jet recording method, and

[0021] applying the liquid composition to at least a part of an image ofthe recorded article to insolubilize the polymer contained in the liquidcomposition on the surface of the image, thereby forming the coatinglayer at a position to which the liquid composition has been applied,

[0022] wherein the recording medium has a surface which insolubilizesthe polymer.

[0023] According to the present invention, there is also provided animage forming process for forming an image-recorded article having acoating layer on an image formed, which comprises the steps of

[0024] providing a liquid composition containing an aqueous medium and apolymer having a structure represented by a general formula

—COOA   (1)

[0025] wherein A is an alkali metal, ammonium or an organic ammonium,

[0026] providing an image-recorded article formed on a recording mediumhaving a surface pH which insolubilizes the polymer by an ink-jetrecording method, and

[0027] applying the liquid composition to the recorded article to formthe coating layer on the image-recorded article.

[0028] According to the present invention, there is further provided animage forming process for forming an image-recorded article having acoating layer on an image formed, which comprises the steps of

[0029] providing a liquid composition containing an aqueous medium and apolymer having a structure represented by a general formula

—COOA   (1)

[0030] wherein A is an alkali metal, ammonium or an organic ammonium,

[0031] providing an image-recorded article formed on a recording mediumcontaining a polyvalent metal ion which insolubilizes the polymer by anink-jet recording method, and

[0032] applying the liquid composition to the recorded article to formthe coating layer on the image-recorded article.

[0033] According to the present invention, there is still furtherprovided a liquid composition for forming a coating layer on at least apart of an image-recorded article formed on a recording medium by anink-jet recording method, which comprises an aqueous medium and apolymer having a structure represented by a general formula

—COOA   (1)

[0034] wherein A is an alkali metal, ammonium or an organic ammonium,

[0035] wherein the polymer is dissolved in the aqueous medium in such astate as to be insolubilized by the surface pH of the recording medium.

[0036] According to the present invention, there is yet still furtherprovided a liquid composition for forming a coating layer on at least apart of an image-recorded article formed on a recording medium by anink-jet recording method, which comprises an aqueous medium and apolymer having a structure represented by a general formula

—COOA   (1)

[0037] wherein A is an alkali metal, ammonium or an organic ammonium,

[0038] wherein the polymer is dissolved in the aqueous medium in such astate as to be insolubilized by a polyvalent metal ion contained in therecording medium.

[0039] According to the present invention, there is yet still furtherprovided an ink-jet recording apparatus comprising a liquid holding partfor holding a liquid therein and a liquid ejecting part for ejecting theliquid fed from the liquid holding part, wherein the liquid is any ofthe liquid compositions described above.

[0040] According to the present invention, there is yet still furtherprovided an image-recorded article obtained by any of the image formingprocesses described above.

[0041] In the present invention, the polymer contained in a dissolvedstate in the liquid composition applied to at least a part of the imageis insolubilized on the surface of the image to form a coating layer.This coating layer can bring about an effect of improving the imagequality and impart good gas resistance and rub-off resistance to theimage. Incidentally, the position of the coating layer formed on theimage is not limited to a colored portion by a coloring material such asa dye, but may be on a non-colored portion alone.

BRIEF DESCRIPTION OF THE DRAWING

[0042]FIG. 1 is a perspective view illustrating an exemplary ink-jetrecording apparatus.

[0043]FIG. 2 schematically illustrates a recording unit containing aliquid composition according to the present invention and recordingunits respectively containing inks of Y, M, C and Bk have been mountedon the same carriage.

[0044]FIG. 3 schematically illustrates a cartridge equipped withcontainer parts respectively containing an ink and a liquid compositionaccording to the present invention.

[0045]FIG. 4 schematically illustrates a recoding head in which thecartridge shown in FIG. 3 has been installed.

[0046]FIG. 5 illustrates, in enlarged scale, of an orifice part of arecording head according to an embodiment in the ink-jet recordingapparatus shown in FIG. 1.

[0047]FIG. 6 typically illustrates a roller coater part of aroller-coating device of a liquid composition according to the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

[0048] The image forming process according to the present invention willhereinafter be described in details.

[0049] (Recording Method)

[0050] A polymer contained in a liquid composition for forming a coatinglayer in the present invention is dissolved in an aqueous medium and isinsolubilized on the surface of a recording medium on which an image hasbeen formed. A preferred embodiment thereof is a mode that the liquidcomposition contains a polymer having a structure represented by ageneral formula

—COOA   (1)

[0051] wherein A is an alkali metal, ammonium or an organic ammonium,and the polymer is insolubilized on the surface of a recording medium onwhich an image has been formed. More specifically, a liquid compositionprepared at a pH higher than that of the surface of the recording mediumis applied on to the recording medium having a pH lower than that of theliquid composition, on which an image has been formed, thereby forming acoating film owing to insolubilization of the polymer in the liquidcomposition. Alternatively, the polymer in the liquid composition may beinsolubilized in a moment on a recording medium, which has been preparedat a polyvalent metal ion concentration at which the polymer isinsolubilized, and on which an image has been formed, thereby forming acoating layer. In other words, the polymer in the liquid applied on theimage is insolubilized in a moment on the image by either process,whereby the polymer and aqueous medium (solvent component) undergosolid-liquid separation, and the aqueous medium component is furtherabsorbed into the recording medium on which the image has been formed,thereby forming the coating layer composed of the insolubilized polymeron the image.

[0052] The present inventors consider the reason why a recorded imagefree of stickiness after formation of the coating layer and good inimage quality, gas resistance and rub-off resistance can be obtained bythe image forming process according to the present invention to be asfollows. When a recording liquid containing a coloring material isejected by an ink-jet recording method to make a record of an image, andthe liquid composition for forming the coating layer is applied to atleast a part of the image formed on a recording medium having a surfacewhich insolubilizes the polymer contained in the liquid composition whenthe liquid composition comes into contact therewith, the polymer isinsolubilized in a moment by an action with the surface of the recordingmedium to undergo solid-liquid separation, so that only the solventcomponent is absorbed into the recording medium to form the coatinglayer on the image. By the formation of this coating layer, the recordedimage is protected from various physical or chemical changes, wherebyhigh gas resistance and image density are imparted to the recordedimage. In addition, even when the coating layer is formed at anon-colored portion on the image, effects such as prevention of stainingare brought about. Preferable examples of the action with the surface ofthe recording medium for insolubilizing the polymer include (1) anaction by pH, (2) an action by a polyvalent metal ion and (3) an actionby combination of both actions (1) and (2) of a polymer having astructure (hereinafter referred to as “carboxylate”) represented by—COOA (1), wherein A is an alkali metal, ammonium or an organicammonium.

[0053] Specifically, according to the action (1) by the pH, the liquidcomposition for forming the coating layer is applied on to an imageformed on a recording medium having a surface pH which insolubilizes thepolymer in the liquid composition by an ink-jet recording system or anyof various ink-coating systems, so that a counter ion of the carboxylatein the polymer is eliminated by an acid possessed by the recordingmedium, on which the image has been formed, to protonize the polymer,whereby the polymer is insolubilized and cohered to form a thin filmhaving high crystallinity.

[0054] Specifically, according to the action (1) by the polyvalent metalion, the polymer-containing liquid composition for forming the coatinglayer is applied on to a recording medium having a surface, which hasbeen prepared at a polyvalent metal ion concentration at which thepolymer dissolved in the liquid composition is insolubilized, by anink-jet recording system or any of various ink-coating systems afterrecording of an image, so that a counter ion of the carboxylate in thepolymer dissolved in the liquid composition is eliminated by apolyvalent metal ion in an ink-receiving layer, so as to associatemolecules of the polymer with each other through the polyvalent metalion, whereby the polymer is insolubilized and cohered to form a thinfilm having high crystallinity. By these actions, the recorded image isprotected from various physical or chemical changes, whereby highfastness properties to gases are imparted to the recorded image.

[0055] The thickness of the coating layer formed on the image in thepresent invention is determined by the amount of the polymer in theliquid composition and the amount of the liquid composition applied perunit area. A preferable thickness of the coating layer is a range offrom 50 to 10,000 nm. If the thickness of the coating layer exceeds theupper limit of this range, the haze of the recorded image is increasedby the presence of such a coating layer, so that the image may becomesuch a state as to be covered with a white mist in some cases. Inaddition, the presence of the film itself may be recognized todeteriorate the quality as a recorded article. If the thickness of thecoating layer is smaller than the lower limit of this range, sufficientgas barrier properties may not be achieved in some cases. When anink-jet system is used as a coating means of the liquid composition, arange of from 50 to 1,000 nm may be mentioned as a more preferable rangeof the thickness of the coating layer. If the thickness of the coatinglayer exceeds the upper limit of this range, the solid concentration ofthe polymer in the liquid composition, which will be describedsubsequently in detail, must be raised, so that problems may be involvedfrom the viewpoints of crusting properties and ejection stability insome cases.

[0056] In the present invention, a constitution that a layer composed ofthe polymer insolubilized by being impregnated into a surface layer ofan image surface is integrated with the coating layer located on theimage surface may be mentioned as a preferred mode. A layer impregnatedwith the polymer is formed in the interior of the surface layer of therecording medium, whereby deterioration of gas resistance by slightflaws or cracks caused in the surface coating layer upon excessscratching or bending can be improved. The thickness of the impregnatedlayer formed in the interior at this time is preferably a range of from0.2 to 10 μm from the surface side. If the thickness of the impregnatedlayer within the recording medium exceeds the upper limit of this range,the quality of the image formed may be deteriorated by haze or whitemist in some cases. If the thickness is smaller than the lower limit ofthis range, the effect by the impregnated layer formed in the interiorof the recording medium may not be achieved in some cases.

[0057] Incidentally, the thicknesses of the coating layer andimpregnated layer in the present invention can be measured byobservation of a section of the recorded article through a scanningelectron microscope.

[0058] In the present invention, no particular limitation is imposed ona means for applying the liquid composition for forming the coatinglayer, which will be described subsequently, on to the image, and ageneral coating method by a roll coater, reverse roll coater or the likeor an ink-jet recording method in the same manner as in a recordingliquid containing a coloring material may be used. The liquidcomposition can be applied on to the recording medium, on which an imagehas been already formed, by any of these applying means. When theink-jet recording method is used, a coating-layer-forming site may bethe whole or only a part of a colored portion (portion colored with acoloring material) of the image formed on the recording medium, thewhole or a part of the image including the colored portion and a portion(non-colored portion) not colored, or the whole or only a part of thenon-colored portion of the image. In particular, the use of the ink-jetrecording method makes easy the control of a position applied and theformation of a thinner and more uniform coating layer. In addition, aseparate provision of a unit for forming the coating layer is madeneedless by adding a nozzle for the liquid composition to an ink-jetrecording head because the method is the same as in the formation of theimage, so that the miniaturization of the whole apparatus is feasible.

[0059] The absorptivities of the liquid composition and recording liquidin the recording medium in the present invention are preferably withinthe following ranges, respectively. With respect to the absorptivity ofthe liquid composition in the recording medium, the absorptioncoefficient, K_(α) 1 from 0.025 seconds to 0.1 seconds in the Bristowmethod prescribed in JAPAN TAPPI No. 51 is preferably within a range offrom 0.5 to 1.5 (ml·m⁻²·msec^(−1/2)). If K_(α) 1 is smaller than 0.5,drying of the coating layer formed may become insufficient to leavestickiness. If K_(α) 1 is greater than 1.5, coloring property of therecording liquid may be lowered in some cases. The cause that thecoloring property is lowered is considered to be attributable to thefact that a coloring material forming an image is pushed out on the backside of the recording medium in a thickness-wise direction thereof withthe penetration of a solvent in the liquid composition. The absorptioncoefficient of the liquid composition in the recording medium can becontrolled by the kind and concentration of such a polymer contained inthe liquid composition as described below, the content of thecarboxylate, the kind of the solvent, the pore diameter and surface pHof a portion of the recording medium, in which an ink is received, andthe like.

[0060] With respect to the absorptivity of the recording liquid in therecording medium, the absorption coefficient, K_(α) 2 from 0.025 secondsto 0.1 seconds in the Bristow method prescribed in JAPAN TAPPI No. 51 ispreferably within a range of from 1.0 to 3.0 (ml·m⁻²·msec^(−1/2)). WhenK_(α) 2 falls within the range of from 1.0 to 3.0 (ml·m⁻²·msec^(−1/2)),such excellent effects that good coloring ability is achieved, beading(aggregation of a dye due to insufficient absorption speed) isprevented, lowering of the coloring ability and image disorder areprevented even when a time difference between recording with therecording liquid containing a coloring material by an ink-jet recordingmethod and application of the liquid composition is short can be broughtabout. The absorption coefficient of the recording liquid in therecording medium can be controlled by the kind and concentration of sucha coloring material as described below, the kind of the solvent,addition of a surfactant, the pore diameter of a portion of therecording medium, in which an ink is received, and the like.

[0061] In the present invention, a ratio, K_(α) 1/K_(α) 2 of bothabsorption coefficients is preferably 0.8 or smaller. When the ratio is0.8 or smaller, the effect of preventing lowering of the coloringability and image disorder can be brought about even when a timedifference between recording with the recording liquid containing acoloring material by an ink-jet recording method and application of theliquid composition is short is made excellent.

[0062] (Liquid Composition)

[0063] The liquid composition for forming the coating layer in thepresent invention will now be described. The polymer contained in theliquid composition is preferably a polymer having a carboxylate. Thepolymer having the carboxylate may be any polymer so far as it is stablydissolved in the liquid composition and can be insolubilized by theaction by the surface pH of the recording medium, the action by thepolyvalent metal ion contained in the recording medium or the combinedaction thereof to form a stable layer. For example, a polymer with avinyl copolymer obtained by using at least one of acrylic monomers suchas acrylic acid, methacrylic acid, maleic acid, a half ester of maleicacid and itaconic acid solubilized with a basic substance is preferred.

[0064] No particular limitation is imposed on the basic substance atthis time. Examples thereof include hydroxides of alkali metals, such aslithium hydroxide, sodium hydroxide and potassium hydroxide, aqueousammonia, monoethanolamine, diethanolamine, triethanolamine,monoisopropanolamine, diisopropanolamine, triisopropanolamine,morpholine, aminomethylpropanol, aminomethylpropanediol, andaminoethylpropanediol.

[0065] The fact that the polymer has the carboxylate structurerepresented by —COOA (1), wherein A is an alkali metal, ammonium or anorganic ammonium, can be confirmed by the following method.

[0066] Namely, this fact can be confirmed by whether absorption based onthe C═O antisymmetric stretching vibration of a carboxylate is presentat from 1550 to 1610 cm⁻¹ in infrared spectrum or not.

[0067] Further, the kind of salt of the carboxylate may be identified byion chromatography, and the kind of salt of the carboxylate can beidentified from the retention time characteristic of a counter ion ofthe carboxylate.

[0068] No particular limitation is imposed on a monomer copolymerizablewith the acrylic monomer so far as it can form a polymer having theintended properties. For example, at least one of the following monomersmay be used. Namely, such monomers include (meth)acrylate monomers suchas methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl(meth)acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate,2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl(meth)acrylate and dodecyl (meth)acrylate. In order to obtain a coatingfilm having a higher gas barrier property, a vinyl copolymer having aunit composed of a monomer containing an aromatic alkyl group oralicyclic alkyl group having optional carbon atoms, preferably 7 to 26carbon atoms is more preferred. Examples of such monomers includestyrene, benzyl (meth)acrylate, 2-anthryl (meth)acrylate,2-(benzoyloxy)-ethyl (meth)acrylate, 2-(5-ethyl-2-pyridyl)ethyl(meth)acrylate, [1,1′-biphenyl]-4-yl (meth)acrylate,7-oxo-1,3,5-cycloheptatoluen-1-yl (meth) acrylate, 8-quinolyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate,1-methylhexyl (meth)acrylate,, 1-methylheptyl (meth)acrylate,2-methylpentyl (meth)acrylate, 1-cyclohexyl-3-azetidinyl (meth)acrylate,9-carbazolylmethyl (meth)acrylate, tetrahydro-2H-pyran-2-yl(meth)acrylate, 3-nitrophenyl (meth)acrylate, 1-(3-pellirenyl)ethyl(meth)acrylate and (3-methyloxiranyl)methyl (meth)acrylate. At least oneselected from these monomers may be used.

[0069] The counter ion (A in the general formula (1)) in the presentinvention includes alkali metals, ammonium and organic ammonium, and atleast one selected from these may be used. Examples of the alkali metalsinclude lithium, sodium, potassium and rubidium. Examples of the organicammonium include alkylammonium and alkanolammonium such asmonoethanolammonium, diethanol-ammonium, triethanolammonium,monoisopropanolammonium, diisopropanolammonium, triisopropanolammonium,monomethylammonium, dimethylammonium, trimethylammonium,monoethylammonium, diethylammonium and triethylammonium.

[0070] In the present invention, at least 2 polymers, which aredifferent in behavior of insolubilization from each other, among thesewater-soluble polymers are preferably contained in the liquidcomposition for the purpose of forming an impregnated layer composed ofa polymer impregnated into the surface layer of the recording medium, onwhich an image has been formed, and insolubilized there under thecoating layer together with the coating layer formed on the surface.These 2 polymers are preferably a combination of (1) at least one ofvinyl copolymers composed of a monomer having an aromatic alkyl group oralicyclic alkyl group and an acrylic monomer and (2) at least one ofvinyl copolymers composed of a monomer containing neither aromatic alkylgroup nor alicyclic alkyl group and an acrylic monomer. Such at least 2water-soluble polymers are contained, whereby layers each formed mainlyof an insolubilized polymer can be provided on the surface of therecording medium and in the interior of the surface layer, respectively.The integral provision of the layers formed of the respective polymerson the surface and in the interior of the surface layer permitsretaining the sufficient gas barrier property even upon excessscratching or bending.

[0071] The reason why the layers can be formed on the surface of therecording medium and in the interior of the surface layer by thecombination of such polymers are not clearly known. However, the presentinventors consider it to be as follows. A state at the time the polymerin the liquid composition is insolubilized greatly participates in theformation of the coating layer. When the polymer is deposited as a bulkysolid upon insolubilization due to its own hydrophobicity, crystallinityor the like, the coating layer is formed on the surface of the recordingmedium, and not formed in the interior of the recording medium. When thepolymer is deposited as a finely particulate dispersion upon theinsolubilization on the other hand, the coating layer is alsoimpregnated into the interior of the surface layer of the recordingmedium to form a layer. More specifically, the vinyl copolymer composedof a monomer having an aromatic alkyl group or alicyclic alkyl group andan acrylic monomer is easy to form a coating layer on the surface of therecording medium, while the vinyl copolymer composed of a monomercontaining neither aromatic alkyl group nor alicyclic alkyl group and anacrylic monomer is easy to form an impregnated layer in the interior ofthe recording medium. It is thus considered that the combined use ofthese 2 polymers permits forming the coating layer on the surface and inthe interior of the recording medium.

[0072] The molecular weight of the polymer having the carboxylateaccording to the present invention is within a range of, for example,from 1,000 to 100,000, preferably from 1,000 to 50,000 in terms of aweight average molecular weight before addition of the basic substance.If the weight average molecular weight exceeds 100,000, the resultingliquid composition tends to have a higher viscosity, and so a uniformfilm may be hard to be provided in some cases. If the weight averagemolecular weight is lower than 1,000 on the other hand, any coatinglayer having a sufficient gas barrier property may not be provided insome cases. The weight average molecular weight in the present inventionis a value in terms of a polystyrene in a mixed solvent of THF/DMF bymeans of GPC (gel permeation chromatography).

[0073] In the present invention, the content of the carboxylate in thepolymer varies according to the kind and concentration of the polyvalentmetal ion contained in a recording medium used, the surface pH andsurface condition of the recording medium, and the kinds of monomersforming the polymer, and is suitably selected so as to be insolubilizedon the recording medium to form a coating layer. For example, when thecoating layer is formed by the action with the polyvalent metal ion, theconcentration of the carboxylate is adjusted in such a manner that whenthe liquid composition containing the polymer having the carboxylate isadded dropwise to an aqueous solution of a polyvalent metal ionconcentration corresponding to the concentration of the polyvalent metalion contained in the ink-receiving layer of the recording medium, thepolymer in the liquid composition is insolubilized and deposited.

[0074] The acid value of the polymer having the carboxylate according tothe present invention is preferably from 50 to 300 when, for example, a(meth)acrylic copolymer is used. If the acid value is lower than 50, aproblem may arises from the viewpoint of the crusting property. When athermal ink-jet system is used in particular, such polymer may form thecause of scorch on a heater so as not to achieve stable ejectionproperties. If the acid value exceeds 300 on the other hand,insolubilization on the recording medium becomes hard to occur, so thatthe surface pH of the recording medium must be extremely lowered, andthe tint of an image formed may become a problem in some cases. The acidvalue in the present invention is measured by a measuring methodaccording to JIS K 0070.

[0075] The glass transition point (Tg) of the polymer having thecarboxylate according to the present invention is preferably within arange from −50 to −130° C., more preferably from −40 to 130° C., stillmore preferably from −20 to 120° C. The Tg satisfies this range, wherebya sticky feel of the coating layer is reduced, and deterioration of gasresistance by cracking or the like caused by bending or the like of thecoating layer can be prevented.

[0076] As a production process of the polymer contained in the liquidcomposition, may be used an ordinary radical polymerization process, andbulk polymerization, suspension polymerization, emulsion polymerizationor the lime may be used. The polymerization is preferably conducted at araw monomer concentration ranging from 15.0 to 35.0% by mass. In thiscase, a general radical polymerization initiator may be used as apolymerization initiator. Among others, an azo compound or peroxidecompound is preferred.

[0077] A monomer having various functions may be contained in thepolymer according to the present invention in addition to theabove-described monomers as needed. For example, a monomer havingultraviolet absorbency may preferably be contained because the lightfastness of a recorded article obtained in the present invention can begreatly improved.

[0078] No particular limitation is imposed on the monomer having theultraviolet absorbency so far as it has an effect of absorbingultraviolet rays. However, a monomer containing a benzotriazolecompound, benzophenone compound or hindered amine compound is suitable.Specifically, at least one of the following monomers may be used.Namely, the monomers include2(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole,2-hydroxy-5-methacryloxyethyl-4-methoxybenzophenone and2-hydroxy-5-methacryloxyethyl-4-octyloxybenzophenone.

[0079] The pH of the liquid composition according to the presentinvention is adjusted by the amount of the basic substance added or witha pH adjustor or the like and must be a pH required that the polymerhaving the carboxylate is solubilized in water. A preferred pH of theliquid composition is within a range of from 5.4 to 11.0. If the pH ofthe liquid composition exceeds 11.0, a problem may arise on durabilityof members coming into contact with such a liquid composition, such as ahead. If the pH of the liquid composition is lower than 5.4, the surfacepH of the recording medium must be extremely lowered, or the polyvalentmetal ion concentration of the recording medium must be extremelyraised, which will be described subsequently. As a result, the tint ofthe resulting image may become a problem. When the means forinsolubilizing the polymer is owing to the action by pH, a differencebetween the pH of the liquid composition and the surface pH of therecording medium, which will be described subsequently, is preferably0.5 or greater, more preferably 1.0 or greater.

[0080] The content of the polymer having the carboxylate in the liquidcomposition is preferably, for example, 1.0 to 15.0% by mass, in termsof a proportion before addition of the basic substance and the like,based on the whole mass of the liquid composition. If the content of thepolymer in the liquid composition exceeds 15.0% by mass, such a liquidcomposition tends to have a higher viscosity, and so crusting may becomea problem in some cases. If the content is lower than 1.0% by mass onthe other hand, any coating layer having sufficient gas barrierproperties may not be provided in some cases. A content ranging from 1.0to 6.0% by mass is particularly preferred.

[0081] As the solvent used in the liquid composition in the presentinvention, may be used an aqueous medium. As the aqueous medium, may beused water alone or a mixed solvent of water and an water-solubleorganic solvent. A particularly preferred solvent is a mixed solventcomposed of water and a water-soluble organic solvent and containing apolyhydric alcohol having an anti-drying effect on an ink as the organicsolvent. As the water, it is preferable to use deionized water insteadof tap water containing various ions.

[0082] Examples of the water-soluble organic solvent used in combinationwith water include alkyl alcohols having 1 to 4 carbon atoms, such asmethyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol,n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and isobutylalcohol; amides such as dimethylformamide and dimethylacetamide; ketonesand keto-alcohols such as acetone and diacetone alcohol; ethers such astetrahydrofuran and dioxane; polyalkylene glycols such as polyethyleneglycol and polypropylene glycol; alkylene glycols the alkylene moiety ofwhich has 2 to 6 carbon atoms, such as ethylene glycol, propyleneglycol, butylene glycol, triethylene glycol, thiodiglycol, hexyleneglycol and diethylene glycol; 1,2,6-hexanetriol; glycerol; lower alkylethers of polyhydric alcohols, such as ethylene glycol methyl (or ethyl)ether, diethylene glycol methyl (or ethyl) ether and triethylene glycolmonomethyl (or monoethyl) ether; N-methyl-2-pyrrolidone; and1,3-dimethyl-2-imidazolidinone. At least one of these solvents may beused.

[0083] Among these water-soluble organic solvents, polyhydric alcoholssuch as diethylene glycol, and lower alkyl ethers of polyhydricalcohols, such as triethylene glycol monomethyl (or monoethyl) ether arepreferred.

[0084] The content of the water-soluble organic solvent in the liquidcomposition may be suitably selected within a range of, for example,from 0 to 90% by mass, preferably from 5 to 70% by mass, in terms of aproportion before addition of the basic substance and the like, based onthe whole mass of the liquid composition, while the content of water maybe suitably selected within a range of, for example, from 9 to 99% bymass, preferably from 50 to 95% by mass, in terms of a proportion beforeaddition of the basic substance and the like, based on the whole mass ofthe liquid composition.

[0085] A surfactant may be contained in the liquid composition. Inparticular, a surfactant containing ethylene oxide is preferablycontained in the liquid composition.

[0086] When the surfactant containing ethylene oxide is contained in theliquid composition, lowering of the gas barrier property is prevented,and the ejection property of the resulting liquid composition whenejected from an ink-jet recording apparatus of a thermal system can beimproved.

[0087] The reason why the lowering of the gas barrier property can beprevented is considered to be attributable to the fact that thesurfactant containing ethylene oxide is adsorbed on the polymer havingthe carboxylate, and the solubility of the polymer in water is enhanced.Therefore, the liquid composition, to which the surfactant containingethylene oxide has been added, suitably controls rapid insolubilizationto increase a leveling property, so that grain boundaries become hard tooccur to provide a coating layer having a high gas barrier property. Thereason why the ejection property can be improved is considered to be asfollows. When the (meth)acrylic copolymer having a low acid value isejected from an ink-jet recording apparatus of a thermal system inparticular, insolubilization or the like occurs on a heater of arecording head by heat upon bubbling due to its low solubility in water,and normal bubbling is prevented by the insoluble matter occurred atthis time. It is however considered that the addition of the surfactantcontaining ethylene oxide enhances the solubility of the polymer inwater to make the polymer hard to be insolubilized, and redissolution iscaused by refilling of an ink after the ejection even when theinsolubilization occurs, so as to normally conduct bubbling.

[0088] The surfactant containing ethylene oxide preferably used in thepresent invention may be any surfactant so far as it has at least 5ethylene oxide chains. Specific examples thereof include polyoxyethylenelauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearylether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether,polyoxyethylene octyl phenyl ether, polyoxyethylene stearylamine andblock copolymers of ethylene oxide and propylene oxide. At least one ofthese surfactants may be used. However, the present invention is notlimited thereby. It is only necessary for the surfactant to have atleast 5 ethylene oxide chains. However, the length of the ethylene oxidechain is preferably within a range of from about 5 to 50 for practicingthe present invention. A more preferable range is from 10 to 50. If theethylene oxide chains of the surfactant used is less than 5, such asurfactant involves a problem that it is not soluble in water. If theethylene oxide chains of the surfactant used is more than 50 on theother hand, reejection property after suspending of the resulting liquidcomposition may be deteriorated in some cases.

[0089] The amount of the surfactant containing ethylene oxide used is0.01 to 20% by mass, preferably 0.1 to 5% by mass. If the amount is lessthan the lower limit of this range, the effect by this surfactant ishard to be brought about. If the amount exceeds the upper limit, of thisrange, the reelection property after ,suspending of the resulting liquidcomposition may be deteriorated in some cases.

[0090] In order to improve the light fastness of a resulting recordedarticle when forming the coating layer of the liquid composition, it ispreferable that the maximum absorption wavelength λ_(max) of the UVabsorption spectrum of the coating layer be present at 400 nm orshorter, and the absorption coefficient “e” in the maximum absorptionwavelength λ_(max) represented by the following equation be from 0.1 to6.0.

A=e·C

[0091] wherein A is an absorbance in the maximum absorption wavelengthλ_(max) of the coating layer, and C is a film thickness (μm) of thecoating layer

[0092] When the absorption coefficient “e” of the coating layer fallswithin a range of from 0.1 to 6.0, the light fastness of the recordedarticle can be improved while keeping the coating layer colorless andtransparent.

[0093] In order to make the absorbance of the coating layer within theabove-described range, it is effective to contain such a monomer havingultraviolet absorbency as described above in the polymer used. However,it may be adjusted by containing an ultraviolet absorbent in the liquidcomposition as needed. To the liquid composition according to thepresent invention, a viscosity modifier, a surface tension modifier, apH adjustor, a mildewproofing agent, a rust-preventing agent, anantioxidant and/or the like may be added in addition to theabove-described components, as needed.

[0094] A coloring material may be contained in the liquid compositionaccording to the present invention for purposes of, for example,ornament (insertion of logo or the like with a pale blue color). In thiscase, the coloring material is present in the coating layer, so that thegas resistance (of the logo or the like) is somewhat poor compared withthe coloring material present in the ink-receiving layer. Accordingly,the concentration of the coloring material in the liquid composition ispreferably 0.5% by mass or less, more preferably 0.2% by mass or less.

[0095] (Recording Medium)

[0096] The recording medium used in the present invention will now bedescribed. In the present invention, the polymer in the liquidcomposition for forming the coating layer is insolubilized on animage-forming surface of a recording medium as described above. When theinsolubilization of the polymer is caused by the action by pH, thesurface pH (for example, concentration of an acid) of the recordingmedium must be controlled to a value required to insolubilize thepolymer in the liquid composition. A specific surface pH of therecording medium may be suitably selected according to the polymer usedin the liquid composition. However, a preferable range of the surface pHis from 4.0 to 7.0, more preferably from 5.4 to 7.0. If the surface pHexceeds the upper limit of this range, the insolubilization of thepolymer in the liquid composition on the recording medium becomes hardto occur, so that the content of the carboxylate in the polymer must belowered. Therefore, sufficient ejection stability may not be achieved insuch a liquid composition. If the surface pH is lower than the lowerlimit of this range, the tint of the coloring material in the resultingrecorded image may be changed, bronzing may occur, or the absorbency ofthe recording medium to a recording liquid (dye ink) may bedeteriorated.

[0097] Methods for adjusting the surface pH of the recording mediuminclude a method, in which an aqueous solution of an acid such as nitricacid, hydrochloric acid or sulfuric acid, or an aqueous solution of analkali such as ammonia is applied to a recording medium having aprescribed surface pH produced in advance by a publicly known process soas to give a desired surface pH, and in the case where an ink-receivinglayer is formed, a method, in which a pH of a coating formulation forforming the ink-receiving layer is adjusted to a desired pH in advance,and such a coating formulation is applied to a base material and driedto form the ink-receiving layer. Incidentally, the surface pH wasmeasured in accordance with the Surface pH Measuring Method of Paper inJAPAN TAPPI No. 49-2 (Coating Process).

[0098] When the insolubilization of the polymer is caused by the actionby the polyvalent metal ion in the recording medium, the concentrationof the polyvalent metal ion in the recording medium forming an imagesurface must be controlled to a value required to insolubilize thepolymer in the liquid composition. It is preferable to use a recordingmedium having an ink-receiving layer and contain the polyvalent metalion in the ink-receiving layer. In this case, a specific concentrationof the polyvalent metal ion in the recording medium may be suitablyselected according to the polymer used in the liquid composition.However, a preferable range of the polyvalent metal ion concentration inthe ink-receiving layer is from 0.01 to 1.0 (mol/l), more preferablyfrom 0.04 to 0.8 (mol/l). If the concentration of the polyvalent metalion concentration in the ink-receiving layer is less than 0.01 mol/l,the acid value of the polymer must be lowered for the purpose ofinsolubilizing the polymer in the liquid composition on the recordingmedium, so that sufficient ejection stability may not be achieved insuch a liquid composition. If the concentration of the polyvalent metalion in the ink-receiving layer exceeds 1.0 mol/l on the other hand, thetint and light fastness of the resulting recorded image and theabsorbency of the recording medium to a recording liquid (dye ink) maybe deteriorated.

[0099] The concentration of the polyvalent metal ion in theink-receiving layer in the present invention is determined in accordancewith the equation Polyvalent metal ion concentration (mol/l)=W/VPwherein W and VP denote a content (mol/g) of the polyvalent metal ionper gram of the ink-receiving layer and a void volume (ml/g) per gram ofthe ink-receiving layer, respectively.

[0100] W in the above equation can be measured by suitably taking theink-receiving layer out of the recording medium and using a fluorescenceX-ray measuring device or the like. VP is determined from a volume (V1(m1/m2)) of the ink-receiving layer per unit area on the recordingmedium, a mass (H1 (g/m2)) of the ink-receiving layer per unit area onthe recording medium and a true density (D1 (ml/g)) of the ink-receivinglayer in accordance with the equation, VP=V1/H1−D1. The true density ofthe ink-receiving layer can be measured by suitably taking theink-receiving layer out of the recording medium and using, for example,a dry automatic densimeter (Accupyc 1330, manufactured by ShimadzuCorporation) or the like. In the case of a recording medium, in which amulti-layer receiving layer has been formed on a base material, themeasurement is made as to the outermost layer to determine therespective values.

[0101] Examples of the polyvalent metal ion in the present inventioninclude polyvalent ions of alkaline earth metals such as magnesium andcalcium, rare earth metals such as yttrium, lanthanum and cerium, andtransition metals such as zirconium. However, any polyvalent metal ionmay be used so far as it can insolubilize the polymer in the liquidcomposition for forming the coating layer. At least one selected fromthese polyvalent metal ions may be used.

[0102] Methods for adding the polyvalent metal ion to the ink-receivinglayer include a method, in which an aqueous solution of a water-solublepolyvalent metal salt is applied to a recording medium produced so as togive a desired polyvalent metal ion concentration, and a method, inwhich a polyvalent metal salt is added into a coating formulation forforming the ink-receiving layer in advance so as to give a desiredpolyvalent metal ion concentration, and such a coating formulation isapplied to a base material and dried to form the ink-receiving layer.

[0103] As the recording medium used in the present invention, may besuitably used that obtained by providing a porous ink-receiving layercomposed mainly of a pigment on a base material.

[0104] No particular limitation is imposed on the base material, and apaper web such as suitably sized paper, water leaf paper or resin-coatedpaper, a sheet-like substance such as a resin film, or cloth may beused. When suitably sized paper or water leaf paper is used as the basematerial in particular, such paper preferably has the same surface pH asthat of the resulting recording medium from the viewpoint of stability.Further, taking the permeation of a gas from the back side thereof intoconsideration, that subjected to gas barrier treatment by lamination orthe like may also be suitably used.

[0105] The ink-receiving layer of the recording medium in the presentinvention is preferably formed in such a manner that the pore volumethereof falls within a range of from 0.35 to 1.0 ml/g, more preferablyfrom 0.4 to 0.9 ml/g. If the pore volume of the ink-receiving layer isgreater than the upper limit of this range, cracking and dusting mayoccur on such an ink-receiving layer in some cases. If the pore volumeof the ink-receiving layer is smaller than the lower limit of thisrange, the absorption of an ink is worsened. When multi-color printingis conducted in particular, inks may overflow the ink-receiving layer insome cases, so that the resulting image may become easy to causebleeding.

[0106] The BET specific surface area of the ink-receiving layer ispreferably within a range of from 50 to 300 m²/g, more preferably from100 to 300 m²/g. If the BET specific surface area is smaller than thelower limit of this range, the gloss of such an ink-receiving layer islost, and the haze thereof is increased, so that white mist may occur onthe resulting image in some cases. If the BET specific surface area isgreater than the upper limit of the range, such an ink-receiving layermay become easy to cause cracking. Incidentally, the BET specificsurface area and pore volume can be determined by the nitrogenadsorption and desorption method after an ink-receiving layer issubjected to a degassing treatment.

[0107] No particular limitation is imposed on a material for forming theink-receiving layer exhibiting the above-described physical properties.However, an alumina hydrate represented by the following general formula(2) may be mentioned as a preferable example from the viewpoints ofcoloring ability and absorbency.

Al₂O₃·n(OH)_(2n)·mH₂O   (2)

[0108] wherein n is an integer of 0, 1, 2 or 3, m is a number of 0 to10, preferably 0 to 5. Incidentally, n and m are not 0 at the same time.In many cases, mH₂O represents an aqueous phase, which does notparticipate in the formation of a crystal lattice, but is able to beeliminated. Therefore, m may take a value other than an integer. Whenthis kind of alumina hydrate is calcined, m may reach a value of 0.

[0109] The pore physical properties of the alumina hydrate are adjustedin the course of the production thereof, and an alumina hydrate having apore volume of 0.3 to 1.0 ml/g, preferably 0.35 to 0.9 ml/g ispreferably used in order to satisfy the above-described BET specificsurface area and pore volume of the ink-receiving layer. The aluminahydrate having a pore volume within this range is more preferred in thatthe pore volume of the resulting ink-receiving layer is controlledwithin the above-described range. With respect to the BET specificsurface area, an alumina hydrate having a BET specific surface area of50 to 350 m²/g, preferably 100 to 250 m²/g is preferably used. Thealumina hydrate having a BET specific surface area within this range ismore preferred in that the BET specific surface area of the resultingink-receiving layer is controlled within the above-described range.

[0110] The coating weight of a dispersion (coating formulation) may be0.5 to 60 g/m², preferably 5 to 45 g/m² in terms of dry solids content.The layer thickness of the ink-receiving layer may be within a range of,for example, from 15 to 60 μm, preferably from 20 to 55 μm, particularlypreferably from 25 to 50 μm for the purpose of achieving good inkabsorbency and resolution.

[0111] (Recording Liquid)

[0112] The recording liquid containing a coloring material in thepresent invention will now be described. In the present invention, thecomponent itself of the coloring material may be a publicly knownmaterial, and examples thereof include water-soluble dyes represented bydirect dyes, acid dyes, basic dyes, reactive dyes and food colors. Sucha water-soluble dye is used in a proportion of about 0.1 to 20% by massin the recording liquid.

[0113] The solvent used for the recording liquid used in the presentinvention is water or a mixed solvent of water and a water-solubleorganic solvent. Those mentioned for the liquid composition for formingthe coating layer are preferably used. The content of the water-solubleorganic solvent in the recording liquid is within a range of generallyfrom 0 to 95% by mass, preferably from 10 to 80% by mass, morepreferably from 15 to 50% by mass based on the whole mass of the ink(recording liquid).

[0114] In the recording liquid used in the present invention, asurfactant, a viscosity modifier, a surface tension modifier, a pHadjustor, a mildewproofing agent, a rust-preventing agent and/or thelike may be added in addition to the above-described components, asneeded.

[0115] <Ink-Jet Recording Apparatus>

[0116] An apparatus having both image-forming section and liquidcomposition-applying section by an ink-jet system will now be described.An ink-jet recording apparatus according to an embodiment of the presentinvention comprises a first recording unit equipped with an inkcontainer part, which contains an ink-containing a coloring material,and an ink-jet head for ejecting the ink and a second recording unitequipped with a liquid composition container part, which contains aliquid composition, and an ink-jet head for ejecting the liquidcomposition. An ink-jet recording apparatus according to anotherembodiment comprises an ink container part, which contains an inkcontaining a coloring material, a liquid composition container part,which contains a liquid composition, and ink-jet heads for independentlyejecting the ink contained in the ink container part and the liquidcomposition contained in the liquid composition container part. Theseapparatus will hereinafter be described.

[0117]FIG. 1 illustrates an exemplary ink-jet recording apparatus. InFIG. 1, reference numeral 61 designates a blade serving as a wipingmember, one end of which is a stationary end held by a blade-holdingmember to form a cantilever. The blade 61 is arranged at a positionadjacent to a region in which a recording head 65 operates. In thisembodiment, the blade 61 is held in such a form that it protrudes intothe course through which the recording head 65 is moved. Referencenumeral 62 indicates a cap for a face of ejection openings of therecording head 65, which is provided at a home position adjacent to theblade 61, and is so constructed that it moves in a directionperpendicular to a direction in which the recording head 65 is moved,and comes into contact with the face of ejection openings to cap it.Reference numeral 63 denotes an ink-absorbing member providedadjoiningly to the blade 61 and, similar to the blade 61, held in such aform that it protrudes into the course through which the recording head65 is moved. The above-described blade 61, cap 62 and ink-absorbingmember 63 constitute an ejection-recovery portion 64, where the blade 61and ink-absorbing member 63 remove water, dust and/or the like from theface of the ink-ejecting openings. Reference numeral 65 designates therecording head having an ejection-energy-generating means and serving toeject the ink onto a recording medium set in an opposing relation to theejection opening face provided with the ejection openings to conductrecording. Reference numeral 66 indicates a carriage on which therecording head 65 is mounted so that the recording head 65 can be moved.The carriage 66 is slidably interlocked with a guide shaft 67 and isconnected (not illustrated) at its part to a belt 69 driven by a motor68. Thus, the carriage 66 can be moved along the guide shaft 67 andhence, the recording head 65 can be moved from a recording region to aregion adjacent thereto. Reference numerals 51 and 52 denote a feedingpart from which the recording media are separately inserted, and feedrollers driven by a motor (not illustrated), respectively. With such aconstruction, the recording medium is fed to the position opposite tothe ejection opening face of the recording head 65, and discharged froma discharge section provided with discharge rollers 53 with the progressof recording.

[0118] In the above construction, the cap 62 in the ejection-recoveryportion 64 is receded from the path of motion of the recording head 65when the recording head 65 is returned to its home position, forexample, after completion of recording, and the blade 61 remainsprotruded into the path of motion. As a result, the ejection openingface of the recording head 65 is wiped. When the cap 62 comes intocontact with the ejection opening face of the recording head 65 to capit, the cap 62 is moved so as to protrude into the path of motion of therecording head 65. When the recording head 65 is moved from its homeposition to the position at which recording is started, the cap 62 andthe blade 61 are at the same positions as the positions for the wipingas described above. As a result, the ejection opening face of therecording head 65 is also wiped at the time of this movement. The abovemovement of the recording head 65 to its home position is made not onlywhen the recording is completed or the recording head 65 is recoveredfor ejection, but also when the recording head 65 is moved betweenrecording regions for the purpose of recording, during which it is movedto the home position adjacent to each recording region at givenintervals, where the ejection opening face is wiped in accordance withthis movement.

[0119] As an example of a cartridge according to the present invention,may be mentioned a cartridge so constructed that it has 2 containerparts separately containing the ink and the liquid composition, whichmake up an ink set according to the present invention, is detachablyinstalled in a recording head for ejecting the ink and the liquidcomposition and can fed the ink and the liquid composition to therecording head. FIG. 3 illustrates an example of such a cartridge 1001.Reference numerals 1003 and 1005 in FIG. 3 indicate an ink containerpart, which contains the ink, and a liquid composition container part,which contains the liquid composition, respectively. This cartridge isso constructed that it is detachably installed in a recording head 1101,from which the ink and the liquid composition can be ejected, asillustrated in FIG. 4, and that the liquid composition and the ink arefed to the recording head 1101 when the cartridge 1001 is installed inthe recording head 1101.

[0120] The ink-jet recording apparatus used in the present invention arenot limited to the apparatus as described above in which the head andthe ink cartridge are separately provided as described above. Therefore,an apparatus in which these members are integrally formed can also bepreferably used.

[0121] Incidentally, as the recording apparatus used in the presentinvention, may be used the ink-jet recording apparatus in which thermalenergy is applied to the ink and the liquid composition to ejectdroplets of the ink and the liquid composition as described above, andan ink-jet recording apparatus of a piezo-system using a piezoelectricelement.

[0122] In the case where the process for forming a colored portion onthe recording medium according to the present invention is carried out,for example, a recording apparatus, in which five recording heads arearranged on a carriage, is used. An example thereof is illustrated inFIG. 2. Reference numerals 81, 82, 83 and 84 indicate recording headsfor ejecting yellow, magenta, cyan and black inks, respectively.Reference numeral 85 designates a head for ejecting the liquidcomposition according to the present invention. The heads are arrangedin the above-described recording apparatus and serve to eject therespective recording inks of the different colors according to recordingsignals. The liquid composition according to the present invention isapplied on to at least a part of an image formed after the ejection ofthe recording inks. FIG. 2 shows the case where the five recording headsare used. However, the present invention is not limited thereto. Asshown in FIG. 5, preference is given even to the case where the flowpaths of the inks of yellow 801Y, magenta 801M, cyan 801C and black801Bk, and the liquid composition 801S are separately provided in onerecording head.

[0123] <Roller-Coating Device>

[0124]FIG. 6 typically illustrates a roller coater part of aroller-coating device. The liquid composition is charged into a tank 42,and the liquid composition is applied to an intermediate coating roller38 by means of a coating member 40 composed of a porous material. Theliquid composition is then applied to a surface of the recording medium,on which an image has been recorded, by means of a coating roller 36.Reference numeral 41 indicates a blade for uniformly applying the liquidcomposition to the coating roller. The liquid composition 39 is suppliedfrom a liquid composition cartridge 43. The coating roller 36 may beformed of a rubber roller, fluororesin-coated roller, felt roller, brushroller or porous roller.

[0125] The present invention will hereinafter be described by thefollowing Examples. Incidentally, all designations of “part” or “parts”and “%” as will be used in the following examples mean part or parts bymass and % by mass unless expressly noted.

EXAMPLES 1 TO 8

[0126] (Preparation 1 of Liquid Composition)

[0127] {Liquid Composition A}

[0128] A styrene-acrylic acid copolymer A (St (styrene)/AA (acrylicacid)=70/30 (% by weight); molecular weight: 10,000; acid value: 201)synthesized by a solution polymerization process using a radicalinitiator was used to prepare Liquid Composition A of the followingcomposition. Incidentally, potassium hydroxide was used as a basicsubstance, and the amount added was controlled in such a manner that thepH of each liquid composition is 8.0. Styrene-acrylic acid copolymer A 3parts Glycerol 7 parts Diethylene glycol 5 parts Water  85 parts. 

[0129] {Liquid Composition B}

[0130] Liquid Composition B was prepared in the same manner as in LiquidComposition A except that the styrene-acrylic acid copolymer was changedas shown in Table 1.

[0131] (Production of Recording Medium)

[0132] {Recording Medium A}

[0133] Disperal HP13 (trade name; product of CONDEA Co.) as an aluminahydrate was mixed with purified water to prepare a dispersion containing5% of solids. Hydrochloric acid was then added to the dispersion toadjust the pH of the dispersion to 4. After stirring the dispersion fora while, the dispersion was heated to 95° C. with stirring and kept for2 hours at the same temperature. The pH of the dispersion was adjustedto 9.5 with caustic soda, and the dispersion was then kept for 8 hourswith stirring. After 8 hours, the temperature of the dispersion wascooled down to room temperature, and the pH thereof was adjusted to 7.2.Thereafter, a desalting treatment was conducted, and acetic acid wasadded to conduct a deflocculating treatment, thereby obtaining colloidalsol. Alumina hydrate obtained by drying the colloidal sol of thisalumina hydrate was determined by X-ray diffractometry and found to havea pseudoboehmite structure. At this time, the BET specific surface areawas 150.2 m²/g, and the pore volume was 0.68 ml/g. Incidentally, thespecific surface area and pore volume were determined by the followingrespective methods.

[0134] 1) Pore volume (PV): determined by means of “AUTOSORB I” (tradename, manufactured by Quantachrome Co.) in accordance with the nitrogenadsorption and desorption method after the sample was subjected to adegassing treatment at 120° C. for 24 hours.

[0135] 2) BET specific surface area (SA): calculated out in accordancewith the method of Brunauer, et al.

[0136] Polyvinyl alcohol PVA117 (trade name, product of Kuraray Co.,Ltd.) was dissolved in purified water to obtain a 9% solution. Colloidalsol of the alumina hydrate obtained above was concentrated to obtain a17% solution. The colloidal sol of the alumina hydrate and the polyvinylalcohol solution were mixed with each other so as to give a weight ratioof 10:1 in terms of solids and stirred to obtain a dispersion.

[0137] After a 5% aqueous solution of sodium borate was applied on to abaryta layer of a base material (surface pH: 6.4) having the barytalayer in advance by an air knife coater so as to give a coating weightof 10 g/m², the above-prepared dispersion was further applied by a diecoater so as to give a dry coating weight of 30 g/m². The base materialused at this time was obtained by applying a baryta composition composedof 100 parts of barium sulfate and 10 parts of gelatin on to a fibrousbase having a basis weight of 150 g/m² and a Stöckigt sizing degree of200 seconds so as to give a dry coating weight of 30 gm² and calendaringit.

[0138] The surface of the ink-receiving layer provided on the basematerial having the baryta layer was subjected to a rewet castingtreatment with hot water (80° C.) by means of a rewet cast coater toobtain a glossy recording medium. Polyethylene was additionallylaminated by an extrusion laminator so as to give a coating weight of 20g/m². The surface pH of the recording medium was 7.2.

[0139] {Recording Media A to D}

[0140] An aqueous solution of nitric acid was applied on to therecording medium obtained in the above-described manner by a wire barand dried to obtain Recording Media A to D whose surface pH was adjustedas shown in Table 1.

[0141] (Examples 1 to 5)

[0142] The liquid compositions and the recording media were combined asshown in Table 1 to make the following evaluation. In each recordedarticle obtained, it was confirmed by observation of its section througha scanning electron microscope that a thin film having its correspondingthickness shown in Table 1 is formed. The results are shown in Table 1.

[0143] (Examples 6 to 8)

[0144] When the content of the styrene-acrylic acid copolymer in LiquidComposition A used in EXAMPLE 1 was changed to 8 parts (LiquidComposition D, EXAMPLE 6), 0.5 parts (Liquid Composition E, EXAMPLE 7)and 0.2 parts (Liquid Composition F, EXAMPLE 8), respectively, thethickness of the thin film layer was changed to 920 nm, 50 nm and 20 nm,respectively.

[0145] (Evaluation Method)

[0146] (Printing)

[0147] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (90% and100%) and secondary color printing (200%) with color inks of thefollowing respective compositions.

[0148] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Water  75 parts.

[0149] Dyes for Inks:

[0150] Y: C.I. Acid Yellow 23

[0151] M: C.I. Acid Red 52

[0152] C: C.I. Direct Blue 199

[0153] Bk: C.I. Food Black 2.

[0154] (Formation of Coating Layer; Ink-Jet Process)

[0155] After printing with the recording liquids respectively containingthe above-described coloring materials, solid printing (200%) with theliquid composition was conducted in the same manner as described aboveso as to completely cover the sites at which solid printing had beenconducted with the respective color inks.

[0156] (Formation of Coating Layer; Coating Process)

[0157] After printing with the recording liquids respectively containingthe above-described coloring materials, the liquid composition wasapplied in an amount of 20 g/m² by a roll coater so as to completelycover the sites at which solid printing had been conducted with therespective color inks.

[0158] (Gas Resistance)

[0159] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of the rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0160] (Tint)

[0161] The tint of the monochromatic solid print portions (90% and 100%)of cyan prepared above was visually evaluated in accordance with thefollowing standard. TABLE 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4Liquid composition Liquid composition A Liquid composition A Liquidcomposition A Liquid composition B St/AA 70/30 70/30 70/30 55/45Molecular weight 10,000 10,000 10,000 12,000 Recording medium RecordingMedium B Recording Medium A Recording Medium C Recording Medium DSurface pH 6.0 7.0 5.4 5.0 Process for forming Ink-jet Ink-jet Ink-jetInk-jet coating layer Thickness of coating 330 290 410 500 layer (nm)Gas resistance (%) 98 98 98 98 Tint A A A B EXAMPLE 5 EXAMPLE 6 EXAMPLE7 EXAMPLE 8 Liquid composition Liquid composition A Liquid composition DLiquid composition E Liquid composition F St/AA 70/30 70/30 70/30 70/30Molecular weight 10,000 10,000 10,000 10,000 Recording medium RecordingMedium B Recording Medium B Recording Medium B Recording Medium BSurface pH 6.0 6.0 6.0 6.0 Process for forming Roll coating Ink-jetInk-jet Ink-jet coating layer Thickness of coating 320 920 50 20 layer(nm) Gas resistance (%) 98 99 90 70 Tint A A A A

EXAMPLES 9 TO 13

[0162] (Preparation of Liquid Composition)

[0163] {Liquid Composition 1A}

[0164] A styrene-acrylic acid copolymer 1A (St/AA=80/20 (% by weight);molecular weight: 10,000; actual acid value: 132) synthesized by asolution polymerization process using a radical initiator was used toprepare Liquid Composition 1A of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and theamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. Styrene-acrylic acid copolymer 1A 3 parts Glycerol 7parts Diethylene glycol 5 parts Water 84 parts BC-30TX (polyoxyethylenecetyl 1 part. ether (EO 30), product of Nippon Surfactant Kogyo K.K.)

[0165] {Liquid Composition 1D}

[0166] Liquid Composition 1D was prepared in the same manner as inLiquid Composition 1A except that a benzyl acrylate-acrylic acidcopolymer 1D (BzA/AA=90/10 (% by weight); molecular weight: 11,000;actual acid value: 70) synthesized by a solution polymerization processusing a radical initiator was used in place of the styrene-acrylic acidcopolymer 1A.

[0167] {Liquid Composition 1E}

[0168] Liquid Composition 1E was prepared in the same manner as inLiquid Composition 1A except that an n-butyl methacrylate-acrylic acidcopolymer 1E (nBMA/AA=80/20 (% by weight); molecular weight: 10,500;actual acid value: 130) synthesized by a solution polymerization processusing a radical initiator was used in place of the styrene-acrylic acidcopolymer 1A.

[0169] {Liquid Composition 1F}

[0170] The n-butyl methacrylate-acrylic acid copolymer 1E was used toprepare Liquid Composition 1F of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and theamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. n-Butyl methacrylate-acrylic acid 3 parts copolymer1E Glycerol 7 parts Diethylene glycol 5 parts Water 84.95 parts   BC-30TX (polyoxyethylene cetyl 0.05 parts.  ether (EO 30), product ofNippon Surfactant Kogyo K.K.)

[0171] {Liquid Composition 1G}

[0172] The n-butyl methacrylate-acrylic acid copolymer 1E was used toprepare Liquid Composition 1G of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and theamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. n-Butyl methacrylate-acrylic acid 3 parts copolymer1E Glycerol 7 parts Diethylene glycol 5 parts Water 84 parts BC-5(polyoxyethylene cetyl 1 part. ether (EO 5), product of NipponSurfactant Kogyo K.K.)

[0173] (Recording Medium)

[0174] The Recording Medium B used in EXAMPLE 1 was used.

[0175] (Evaluation Method)

[0176] (Printing)

[0177] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (100%)with color inks of the following respective compositions, and solidprinting (200%) was then conducted with the liquid composition so as tocompletely cover the sites at which solid printing had been conductedwith the respective color inks.

[0178] Ink Composition: Dye (Y, M C or Bk) 4 parts Ethylene glycol 5parts Glycerol 10 parts  Ethyleneurea 5 parts Water  76 parts. 

[0179] Dyes for Inks:

[0180] Y: C.I. Direct Yellow 86

[0181] M: C.I. Acid Red 52

[0182] C: C.I. Direct Blue 199

[0183] Bk: C.I. Food Black 2.

[0184] (Gas Resistance)

[0185] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of the rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0186] (Ejection Stability)

[0187] An ink-jet recording head evaluation apparatus CANVAS (tradename, manufactured by Canon Inc.) and a printing head for Canon PrinterBJF-660 were used to judge the scatter of ejection velocity between therespective inks under the same conditions as head driving conditions forprinting by the printer.

[0188] A: At most 1 m/s;

[0189] B: 1 to 2 m/s;

[0190] C: 2 to 4 m/s;

[0191] D: At least 4 m/s.

[0192] The above evaluation was made by combining the liquid compositionand the recording medium as shown in Table 2. TABLE 2 EXAMPLE 9 EXAMPLE10 EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 Liquid Liquid Liquid Liquid LiquidLiquid composition Composition Composition Composition CompositionComposition 1A 1D 1E 1F 1G Recording Recording Recording RecordingRecording Recording medium Medium B Medium B Medium B Medium B Medium BGas 98 99 85 80 80 resistance (%) Ejection A A A B B stability

EXAMPLES 14 TO 19

[0193] (Preparation of Liquid Composition)

[0194] {Liquid Composition 2A}

[0195] An n-butyl acrylate-acrylic acid copolymer (nBA/AA=85/15 (% byweight); molecular weight: 10,000) and a styrene-acrylic acid copolymer(St/AA=70/30 (% by weight); molecular weight: 10,000) synthesized by asolution polymerization process using a radical initiator were used toprepare Liquid Composition 2A of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and theamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. n-Butyl acrylate-acrylic acid 1.5 parts copolymerStyrene-acrylic acid copolymer 1.5 parts Glycerol   7 parts Diethyleneglycol   5 parts Water   85 parts.

[0196] {Liquid Compositions 2D and 2E}

[0197] Liquid Compositions 2D and 2E were prepared in the same manner asin Liquid Composition 2A except that the amount of the n-butylacrylate-acrylic acid copolymer was changed as shown in Table 3.

[0198] (Recording Medium)

[0199] Recording Media A to C respectively used in EXAMPLEs 1 to 3 wereused.

[0200] (Examples 14 to 16)

[0201] The liquid compositions and the recording media were combined asshown in Table 4 to make the following evaluation. In each recordedarticle obtained, it was confirmed by observation of its section througha scanning electron microscope that a coating layer on the surface andan impregnated layer into the surface layer, which have theircorresponding thicknesses shown in Table 4, are formed. The results areshown in Table 4.

[0202] (Examples 17 to 18)

[0203] The content of the n-butyl acrylate-acrylic acid copolymer inLiquid Composition 2A used in EXAMPLE 14 was changed to 8 parts (LiquidComposition 2D, EXAMPLE 17) and 0.5 parts (Liquid Composition 2E,EXAMPLE 18), respectively, to make the following evaluation incombination with the respective recording media shown in Table 4. Theresults are shown in Table 4.

[0204] (Liquid Composition 2F)

[0205] Liquid Composition 2F was prepared in the same manner as inLiquid Composition 2A except that the n-butyl acrylate-acrylic acidcopolymer in Liquid Composition 2A used in EXAMPLE 14 was changed to a2-ethylhexyl acrylate-acrylic acid copolymer (2EHA/AA=85/15 (% byweight); molecular weight: 10,000).

[0206] (Example 19)

[0207] The liquid composition and the recording medium were combined asshown in Table 4 to make the following evaluation. The results are shownin Table 4.

EXAMPLE 20

[0208] After printing on Recording Medium B, Liquid Composition 2A wasapplied by a wire bar. At this time, it was confirmed that a coatinglayer having a thickness of 0.9 μm and an impregnated layer having athickness of 1.1 μm are formed on the surface and in the interior of thesurface layer, respectively. This recorded article was evaluated by thefollowing respective evaluation methods. As a result, the gas resistancewas 98%, and the rub-off resistance, tint, resistance to bleeding andstickiness on the surface of the image were all good (A).

[0209] (Evaluation Method)

[0210] (Printing)

[0211] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal-energy to the ink in response torecording signals, was used to conduct momochromatic printing (90% and100%) and secondary color printing (200%) with color inks of thefollowing respective compositions, and solid printing (200%) with theliquid composition was then conducted in the same manner as describedabove so as to completely cover the sites at which solid printing hadbeen conducted with the respective color inks.

[0212] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Water  75 parts.

[0213] Dyes for Inks:

[0214] Y: C.I. Acid Yellow 23

[0215] M: C.I. Acid Red 52

[0216] C: C.I. Direct Blue 199

[0217] Bk: C.I. Food Black 2.

[0218] (Gas Resistance)

[0219] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of the rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0220] (Rub-Off Resistance)

[0221] After the monochromatic solid print portion (100%) of blackprepared above was rubbed 5 times with silbon paper under a load of 40g/cm², the above-described test as to the gas resistance was conductedto visually evaluate it as to the rub-off resistance in accordance withthe following standard.

[0222] A: No scratch-like discoloration occurred at the rubbed portion;

[0223] B: Scratch-like discoloration was slightly observed at the rubbedportion, but it was not observed when viewed 30 cm away;

[0224] C: Scratch-like discoloration was observed at the rubbed portioneven when viewed 30 cm away.

[0225] (Tint)

[0226] The tint of the monochromatic solid print portions (90% and 100%)of cyan prepared above was visually evaluated in accordance with thefollowing standard.

[0227] A: The tint was not changed at the 100% cyan solid-print portion;

[0228] B: The tint was not changed at the 90% cyan solid print portion;

[0229] C: The tint was somewhat reddish at the 90% cyan solid printportion. TABLE 3 Polymer 1 Polymer 2 Molecular Amount added MolecularComposition weight (parts) Composition weight Amount added Liquid nBA/AA= 10,000 1.5 St/AA = 10,000 1.5 Composition 85/15 70/30 2A Liquid nBA/AA= 10,000 8 St/AA = 10,000 1.5 Composition 85/15 70/30 2D Liquid nBA/AA =10,000 0.5 St/AA = 10,000 1.5 Composition 85/15 70/30 2E Liquid 2EHA/AA= 9,000 1.5 St/AA = 10,000 1.5 Composition 85/15 70/30 2F

[0230] TABLE 4 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Liquid 2A 2A 2A2D 2E 2F composition Recording B A C B B B medium Surface pH 6 7 5.4 6 66 Thickness 0.3 0.12 0.4 0.3 0.3 0.3 of coating layer on recordingmedium surface (μm) Thickness 1 1.3 0.8 1.4 0.2 0.4 of impreg- natedlayer formed within surface layer on recording medium surface (μm) Gas98 98 98 99 95 94 resistance Rub-off A A A A B A resistance Tint A A A AA A

EXAMPLES 21 TO 26 AND COMPARATIVE EXAMPLES 1 to 3

[0231] <Recording Medium>

[0232] Recording Medium B used in EXAMPLE 1 was used.

[0233] <Preparation Example of Water-Soluble High-Molecular CopolymerRelated to Liquid Composition>

[0234] Preparation Example 3-1:

[0235] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of propylene glycol monomethyl ether (hereinafterabbreviated as “PGM”) that is a polymerization solvent, and the contentswere heated to the reflux temperature while introducing nitrogen gas andstirring them. A dropping funnel charged with 70.0 g of benzylmethacrylate and 30.0 g of methacrylic acid was separately provided. Inaddition, a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 29.1 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a colorless and transparent solution. The actualacid value and weight average molecular weight of the polymer were 172and 9,700, respectively.

[0236] Preparation Example 3-2:

[0237] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 80.0 g ofcyclohexyl acrylate and 20.0 g of acrylic acid was separately provided.In addition, a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 23.1 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a colorless and transparent solution. The actualacid value and weight average molecular weight of the polymer were 126and 7,100, respectively.

[0238] Preparation Example 3-3:

[0239] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 68.0 g ofstyrene and 32.0 g of acrylic acid was separately provided. In addition,a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 18.5 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a pale yellow and transparent solution. The actualacid value and weight average molecular weight of the polymer were 205and 7,900, respectively.

[0240] Preparation Example 3-4:

[0241] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 84.0 g ofbutyl methacrylate and 16.0 g of acrylic acid was separately provided.In addition, a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 37.0 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a pale yellow and transparent solution. The actualacid value and weight average molecular weight of the polymer were 115and 9,500, respectively.

[0242] Preparation Example 3-5:

[0243] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 65 g ofstyrene, 15 g of n-butyl acrylate and 20 g of acrylic acid wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 23.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a pale yellow and transparentsolution. The actual acid value and weight average molecular weight ofthe polymer were 145 and 10,500, respectively.

[0244] Preparation Example 3-6:

[0245] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 85 g ofn-butyl acrylate and 15 g of acrylic acid was separately provided. Inaddition, a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 17.3 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a pale yellow and transparent solution. The actualacid value and weight average molecular weight of the polymer were 108and 10,200, respectively.

[0246] <Preparation of Liquid Composition for Ink-Jet Recording>

[0247] Liquid Composition 31:

[0248] The preparation of a liquid composition was conducted in thefollowing manner. Namely, the water-soluble high-molecular copolymerobtained in Preparation Example 3-1 was mixed with glycerol, diethyleneglycol, trimethylolpropane and ion-exchanged water at a mass ratiodescribed below, and the resultant mixture was stirred for 30 minutes.Thereafter, the mixture was filtered through a membrane filter having apore size of 0.2 μm to prepare Liquid Composition 31.

[0249] Glycerol: 7%

[0250] Diethylene glycol: 5%

[0251] Trimethylolpropane: 7%

[0252] Water-soluble high-molecular copolymer obtained in PreparationExample 3-1: 3% (in terms of solids concentration of the polymer)

[0253] Ion-exchanged water: 78%.

[0254] The following Liquid Compositions 32 to 35 were prepared inaccordance with the preparation process of Liquid Composition 31.

[0255] Liquid Composition 32:

[0256] Glycerol: 7%

[0257] Diethylene glycol: 5%

[0258] Trimethylolpropane: 7%

[0259] Water-soluble high-molecular copolymer obtained in PreparationExample 3-2: 3% (in terms of solids concentration of the polymer)

[0260] Ion-exchanged water: 78%.

[0261] Liquid Composition 33:

[0262] Glycerol: 7%

[0263] Diethylene glycol: 5%

[0264] Trimethylolpropane: 7%

[0265] Water-soluble high-molecular copolymer obtained in PreparationExample 3-3: 3% (in terms of solids concentration of the polymer)

[0266] Ion-exchanged water: 78%.

[0267] Liquid Composition 34:

[0268] Glycerol: 7%

[0269] Diethylene glycol: 5%

[0270] Trimethylolpropane: 7%

[0271] Water-soluble high-molecular copolymer obtained in PreparationExample 3-4: 3% (in terms of solids concentration of the polymer)

[0272] Ion-exchanged water: 78%.

[0273] Liquid Composition 35:

[0274] Glycerol: 7%

[0275] Diethylene glycol: 5%

[0276] Trimethylolpropane: 7%

[0277] Water-soluble high-molecular copolymer obtained in PreparationExample-3-5: 3% (in terms of solids concentration of the polymer)

[0278] Ion-exchanged water: 78%.

[0279] Liquid Composition 36:

[0280] Glycerol: 7%

[0281] Diethylene glycol: 5%

[0282] Trimethylolpropane: 7%

[0283] Water-soluble high-molecular copolymer obtained in PreparationExample 3-6: 3% (in terms of solids concentration of the polymer)

[0284] Ion-exchanged water: 78%

[0285] Liquid Composition 37 was prepared by using POVAL having apolymerization degree of 100 in accordance with the followingcomposition.

[0286] Liquid Composition 37:

[0287] Glycerol: 7%

[0288] Diethylene glycol: 5%

[0289] Trimethylolpropane: 7%

[0290] POVAL: 3% (in terms of solids concentration of the polymer)

[0291] Ion-exchanged water: 78%.

[0292] (Examples 21 to 26 and Comparative Example 1)

[0293] Liquid Compositions 31 to 37 were evaluated according to thefollowing method. The results are shown in Table 5.

[0294] Comparative Example 2:

[0295] Recording Medium B was used as a blank as it is (without applyingany liquid composition).

[0296] (Evaluation Method)

[0297] (Printing)

[0298] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (100%) andsecondary color printing (200%) with color inks of the followingrespective compositions, and solid printing (200%) was then conductedwith the liquid composition so as to completely cover the sites at whichsolid printing had been conducted with the respective color inks.Further, solid printing (200%) with the liquid composition was alsoconducted on a non-printed portion.

[0299] Ink Composition: Dye (Y, M C or Bk) 4 parts Ethylene glycol 5parts Glycerol 10 parts  Ethyleneurea 5 parts Water  76 parts. 

[0300] Dyes for Inks:

[0301] Y: C.I. Direct Yellow 86

[0302] M: C.I. Acid Red 52

[0303] C: C.I. Direct Blue 199

[0304] Bk: C.I. Food Black 2.

[0305] (Gas Resistance)

[0306] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone-exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0307] TABLE 5 Example Liquid composition Gas resistance EXAMPLE 21Liquid Composition 31 99 EXAMPLE 22 Liquid Composition 32 99 EXAMPLE 23Liquid Composition 33 98 EXAMPLE 24 Liquid Composition 34 72 EXAMPLE 25Liquid Composition 35 95 EXAMPLE 26 Liquid Composition 36 70 COMP.EXAMPLE 1 Liquid Composition 37 31 COMP. EXAMPLE 2 Blank 19

EXAMPLE 27 AND COMPARATIVE EXAMPLE 3

[0308] Liquid compositions containing the high-molecular copolymerobtained in Preparation Example 3-1 in amounts of 1.0 part, 3.0 partsand 6.0 parts respectively were prepared in accordance with thefollowing respective compositions (EXAMPLE 27).

[0309] The liquid composition containing the high-molecular copolymerobtained in Preparation Example 3-1 in an amount of 1.0 part wasprepared in accordance with the following composition.

[0310] Glycerol: 7%

[0311] Diethylene glycol: 5%

[0312] Trimethylolpropane: 7%

[0313] Water-soluble high-molecular copolymer obtained in PreparationExample 3-1: 1% (in terms of solids concentration of the polymer)

[0314] Ion-exchanged water: 80%.

[0315] The liquid composition containing the high-molecular copolymerobtained in Preparation Example 3-1 in an amount of 6.0 parts wasprepared in accordance with the following composition.

[0316] Glycerol: 7%

[0317] Diethylene glycol: 5%

[0318] Trimethylolpropane: 7%

[0319] Water-soluble high-molecular copolymer obtained in PreparationExample 3-1: 6% (in terms of solids concentration of the polymer)

[0320] Ion-exchanged water: 75%.

[0321] Liquid compositions (COMPARATIVE EXAMPLE 3) containing poval(polymerization degree: 100) were prepared in the same manner as inEXAMPLE 27. The liquid compositions and the recording medium werecombined to conduct the above-described evaluation. The results areshown in Table 6. TABLE 6 Concentration of high-molecular High-molecularcopolymer copolymer (parts) Gas resistance EXAMPLE 27 High-molecular 1.098 copolymer 3.0 99 obtained in 6.0 99 Preparation Example 3-1COMPARATIVE POVAL 1.0 28 EXAMPLE 3 (polymerization 3.0 31 degree: 100)6.0 32

EXAMPLES 28 TO 31 AND COMPARATIVE EXAMPLE 4

[0322] <Recording Medium>

[0323] Recording Medium B used in EXAMPLE 1 was used.

[0324] <Preparation Example of Water-Soluble High-Molecular CopolymerRelated to Liquid Composition>

[0325] Preparation Example 4-1:

[0326] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 69.0 g ofstyrene, 30.0 g of methacrylic acid and 1.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a colorless and transparentsolution.

[0327] Preparation Example 4-2:

[0328] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 65.0 g ofstyrene, 30.0 g of methacrylic acid and 5.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a colorless and transparentsolution.

[0329] Preparation Example 4-3:

[0330] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 60.0 g ofstyrene, 30.0 g of methacrylic acid and 10.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a pale yellow and transparentsolution.

[0331] Preparation Example 4-4:

[0332] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 50.0 g ofstyrene, 30.0 g of methacrylic acid and 20.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a pale yellow and transparentsolution.

[0333] Example 28:

[0334] <Preparation of Liquid Composition>

[0335] The preparation of a liquid composition was conducted in thefollowing manner. Namely, the water-soluble high-molecular copolymerobtained in Preparation Example 4-1 was mixed with glycerol, diethyleneglycol, trimethylolpropane and ion-exchanged water at a mass ratiodescribed below, and the resultant mixture was stirred for 30 minutes.Thereafter, the mixture was filtered through a membrane filter having apore size of 0.2 μm to prepare Liquid Composition 41.

[0336] An ink-jet printer (BJF870, trade name, manufactured by CanonInc.) was used to conduct momochromatic printing (100%) on RecordingMedium B prepared above with color inks of the following respectivecompositions, and solid printing (200%) with the liquid composition wasthen conducted so as to completely cover the sites at which solidprinting had been conducted with the respective color inks. Thethus-obtained recorded article was evaluated as to gas resistance andlight fastness. Further, UV absorption spectrophotometry was alsoconducted.

[0337] Liquid Composition 41:

[0338] Glycerol: 7%

[0339] Diethylene glycol: 5%

[0340] Trimethylolpropane: 7%

[0341] Water-soluble high-molecular copolymer obtained in PreparationExample 4-1: 4% (in terms of solids concentration of the polymer)

[0342] Ion-exchanged water: 77%.

[0343] (Gas Resistance)

[0344] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0345] <Light Fastness>

[0346] The monochromatic solid print portion (100%) of magenta preparedabove was subjected to an exposure test as to light fastness by means ofa fluorescent lamp light fastness tester under the following conditions.The light fastness was evaluated in terms of a rate (%) of change of theimage density after the light fastness test.

Light fastness (%)=(Image density after the fluorescent lamp test/Imagedensity before the fluorescent lamp test)×100 (%)

[0347] Test Conditions:

[0348] Light quantity irradiated: 70 klx

[0349] Test time: 620 hours

[0350] Temperature and humidity within test chamber: 24° C., 60% RH

[0351] Filter: soda lime.

[0352] <UV Absorption Spectrophotometry>

[0353] Liquid Composition 41 prepared above was applied on to a PET filmto form a thin film; and a UV absorption spectrum (U-3300, manufacturedby Hitachi Ltd.) was measured by using the PET film as a blank. As aresult, the maximum absorption wavelength was 338.5 nm, and theabsorbance was 0.15. Further, as a result of observation through SEM,the film thickness was found to be 0.48 μm, so that the absorptivitycoefficient “e” calculated out therefrom was 0.31.

[0354] (Examples 29 to 31)

[0355] The following liquid compositions were prepared in accordancewith the preparation process of Liquid Composition 41.

[0356] Liquid Composition 42:

[0357] Glycerol: 7%

[0358] Diethylene glycol: 5%

[0359] Trimethylolpropane: 7%

[0360] Water-soluble high-molecular copolymer obtained in PreparationExample 4-2: 4% (in terms of solids concentration of the polymer)

[0361] Ion-exchanged water: 77%.

[0362] Liquid Composition 43:

[0363] Glycerol: 7%

[0364] Diethylene glycol: 5%

[0365] Trimethylolpropane: 7%

[0366] Water-soluble high-molecular copolymer obtained in PreparationExample 4-3: 4% (in terms of solids concentration of the polymer)

[0367] Ion-exchanged water: 77%.

[0368] Liquid Composition 44:

[0369] Glycerol: 7%

[0370] Diethylene glycol: 5%

[0371] Trimethylolpropane: 7%

[0372] Water-soluble high-molecular copolymer obtained in PreparationExample 4-4: 4% (in terms of solids concentration of the polymer)

[0373] Ion-exchanged water: 77%.

[0374] Liquid Compositions 42 to 44 were also evaluated in the samemanner as in EXAMPLE 28.

[0375] Comparative Example 4:

[0376] Evaluation was conducted in the same manner as in EXAMPLE 28except that no liquid composition was applied.

[0377] Evaluation results as to the gas resistance and light-fastness inEXAMPLEs 28 to 31 are shown together with the results of COMPARATIVEEXAMPLE 4 in Table 7. TABLE 7 Light Example Liquid composition Gasresistance fastness EXAMPLE 28 Liquid Composition 41 98 76 EXAMPLE 29Liquid Composition 42 98 79 EXAMPLE 30 Liquid Composition 43 98 80EXAMPLE 31 Liquid Composition 44 98 81 COMPARATIVE Blank 19 73.5 EXAMPLE4

[0378] As apparent from Table 7, the liquid compositions for ink-jetrecording respectively containing the high-molecular copolymers obtainedin Preparation Examples 4-1 to 4-4 were applied, whereby excellent lightfastness was achieved.

[0379] The results that each liquid composition was applied on to thePET film to form a thin film, and a UV absorption spectrum was measuredto calculate out the maximum absorption wavelength and the absorptivitycoefficient are shown in Table 8. TABLE 8 λ_(max) Absorptivitycoefficient EXAMPLE 28 338.5 0.31 EXAMPLE 29 338.5 1.56 EXAMPLE 30 338.53.01 EXAMPLE 31 338.5 5.98 COMP. EXAMPLE 4 No absorption appeared at 400nm or shorter

EXAMPLES 32 TO 40

[0380] (Preparation 5 of Liquid Composition)

[0381] {Liquid Composition 5A}

[0382] A styrene-acrylic acid copolymer 5A (St/AA=70/30 (% by weight);molecular weight:. 10,500; acid value: 206) synthesized by a solutionpolymerization process using a radical initiator was used to prepareLiquid Composition 5A of the following composition. Incidentally,potassium hydroxide was used as a basic substance, and the amount addedwas controlled in such a manner that the pH of each liquid compositionis 8.0. Styrene-acrylic acid copolymer 6A  3 parts Glycerol  7 partsDiethylene glycol  5 parts Water 85 parts.

[0383] {Liquid Compositions 5B and 5C}

[0384] Liquid Compositions 5B and 5C were prepared in the same manner asin Liquid Composition 5A except that the styrene-acrylic acid copolymerwas changed as shown in Table 9. In Table 9, St and AA indicate astyrene monomer and acrylic acid monomer, respectively.

[0385] (Production of Recording Medium)

[0386] {Recording Medium 5A}

[0387] Aluminum sec-butoxide was prepared in accordance with the processdescribed in U.S. Pat. No. 4,242,271. A 75% mixed solution of thisaluminum sec-butoxide in sec-butyl alcohol was hydrolyzed at 85° C. witha mixed solution of sec-butyl alcohol containing 30% of water to obtainan alumina slurry. After the alumina slurry Was aged at 125° C. for 3hours in an electromagnetically stirring autoclave, water wasimmediately added to the alumina slurry until a solids content was 20%,and the thus-treated alumina slurry was cooled. The pH of the aluminaslurry was adjusted with a 3.8% aqueous solution of nitric acid toobtain Alumina Hydrate 6A. Alumina hydrate A obtained by dryingcolloidal sol of this alumina hydrate was determined by X-raydiffractometry and found to have a pseudoboehmite structure. At thistime, the BET specific surface area was 175 m²/g, and the pore volumewas 0.65 ml/g. Incidentally, the specific surface area and pore volumewere determined by the following respective methods.

[0388] 1) Pore volume (PV): determined by means of “AUTOSORB I” (tradename, manufactured by Quantachrome Co.) in accordance with the nitrogenadsorption and desorption method after a sample was subjected to adegassing treatment at 120° C. for 24 hours.

[0389] 2) BET specific surface area (SA): calculated out in accordancewith the method of Brunauer, et al.

[0390] Polyvinyl alcohol PVA117 (trade name, product of Kuraray Co.,Ltd.) was dissolved in purified water to obtain a 9% solution. Colloidalsol of the alumina hydrate A was concentrated to obtain a 17% solution.The colloidal sol of the alumina hydrate A and the polyvinyl alcoholsolution were mixed with each other so as to give a weight ratio of 10:1in terms of solids and stirred to obtain a dispersion. After a 5%aqueous solution of sodium borate was applied on to a baryta layer of abase material having the baryta layer in advance by an air knife coaterso as to give a coating weight of 10 g/m², the above-prepared dispersionwas further applied by a die coater so as to give a dry coating weightof 30 g/m². The base material used at this time was obtained by applyinga baryta composition composed of 100 parts of barium sulfate and 10parts of gelatin on to a fibrous base having a basis weight of 150 g/m²and a Stöckigt sizing degree of 200 seconds so as to give a dry coatingweight of 30 g/m² and calendaring it.

[0391] The surface of the ink-receiving layer provided on the basematerial having the baryta layer was subjected to a rewet castingtreatment with hot water (80° C.) by means of a rewet cast coater toobtain a glossy recording medium. Polyethylene was additionallylaminated on a back side of the base material by an extrusion laminatorso as to give a coating weight of 20 g/m². The surface pH of therecording medium was 7.2.

[0392] An aqueous solution of nitric acid was applied on to therecording medium obtained in the above-described manner by a wire barand dried to obtain Recording Medium 5A.

[0393] {Recording Media 5B to 5D}

[0394] Recording Media 5B to 5D were obtained in the same manner as inRecording Medium 5A except that alumina hydrates 5B to 5D obtained bychanging the temperature and aging time upon the synthesis of thealumina hydrate used in Recording Medium 5A as shown in Table 10 wererespectively used.

[0395] (Preparation of Recording Liquid Containing Coloring Material)

[0396] {Recording Liquid 5A}

[0397] Recording Liquid 5A of the following composition was prepared.

[0398] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Water 75 parts.

[0399] Dyes for Inks:

[0400] Y: C.I. Acid Yellow 23

[0401] M: C.I. Acid Red 52

[0402] C: C.I. Direct Blue 199

[0403] Bk: C.I. Food Black 2.

[0404] {Recording Liquid 5B}

[0405] Recording Liquid 5B of the following composition was prepared.

[0406] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Acetylenol EH (product of Kawaken  2parts Fine Chemicals Co., Ltd.) Water 73 parts.

[0407] Dyes for Inks:

[0408] Y: C.I. Acid Yellow 23

[0409] M: C.I. Acid Red 52

[0410] C: C.I. Direct Blue 199

[0411] Bk: C.I. Food Black 2.

[0412] The liquid compositions, recording liquids, recording media andcoating layer forming process were combined as shown in Tables 9, 10 and11 to conduct the following evaluation.

[0413] (Evaluation Method)

[0414] (Printing)

[0415] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (100%) andsecondary color printing (200%) with color inks of the above-describedrespective compositions.

[0416] (Formation of Coating Layer; Ink-Jet Process)

[0417] Upon elapsed time of 5 seconds and 60 seconds after printing withthe recording liquids respectively containing the above-describedcoloring materials, solid printing (200%) with the liquid compositionwas conducted in the same manner as described above so as to completelycover the sites at which solid printing had been conducted with therespective color inks.

[0418] (Formation of Coating Layer; Coating Process)

[0419] Upon elapsed time of 5 seconds and 60 seconds after printing withthe recording liquids respectively containing the above-describedcoloring materials, the liquid composition was applied in an amount of20 g/m² by a roll coater (RC) so as to completely cover the sites atwhich solid printing had been conducted with the respective color inks.

[0420] (Gas Resistance)

[0421] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0422] (Stickiness of Coating Layer)

[0423] A sticky feel of each image-recorded article after formation ofthe coating layer produced above was evaluated in accordance with thefollowing standard.

[0424] A: No sticky feel existed after 20 seconds from formation of thecoating layer;

[0425] B: A sticky feel somewhat existed after 20 seconds from formationof the coating layer, but disappeared after 60 seconds;

[0426] C: A sticky feel existed even after 60 seconds from formation ofthe coating layer.

[0427] (Coloring Ability)

[0428] OD (optical density) of the monochromatic solid print portion(100%) of black in each image-recorded article after formation of thecoating layer produced above was measured (by 310TR manufactured byX-Rite Co.).

[0429] (Bleeding)

[0430] Bleeding at an edge portion of each solid printed image formedabove was visually evaluated in accordance with the following standard.

[0431] A: No bleeding occurred in the secondary solid printing (200%);

[0432] B: No bleeding occurred in the monochromatic solid printing(100%);

[0433] C: Bleeding occurred in the monochromatic solid printing (100%)

[0434] (Beading)

[0435] Beading of each solid printed image formed above was visuallyevaluated in accordance with the following standard.

[0436] A: No beading occurred in the secondary solid printing (200%);

[0437] B: No beading occurred in the monochromatic solid printing(100%);

[0438] C: Beading occurred in the monochromatic solid printing (100%).TABLE 9 Liquid composition 5A 5B 5C St/AA 70/30 62/38 55/45 Acid value206 252 297 Molecular weight 10,500 9,000 13,000

[0439] TABLE 10 Recording medium 5A 5B 5C 5D Alumina hydrate 5A 5B 5C 5DBET specific 175 198 227 149 surface area (m²/g) Pore volume (ml/g) 0.650.57 0.51 0.7

[0440] TABLE 11 Example Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 Ex. 37 Ex. 38Ex. 39 Ex. 40 Liquid 5A 5B 5B 5B 5B 5C 5A 5A 5C composition Recording 5A5A 5B 5A 5A 5B 5A 5A 5A liquid Recording 5A 5B 5B 5C 5D 5B 5A 5C 5Bmedium Kα1 1 1.1 1.1 0.5 1.5 0.8 1 0.3 2 Kα2 2.5 1.5 1. 0.5 3 1 2.5 0.51.5 Kα1/Kα2 0.4 0.73 1.1 1 0.5 0.8 0.4 0.6 1.3 Coating IJ IJ IJ IJ IJ IJRC IJ IJ layer forming process (after 5 seconds) Gas 99% 99% 99% 99% 99%99% 99% 99% 99% resistance Sticky feel A A A A A A A B A OD 2.12 2.281.95 2.22 2.04 2.00 2.12 2.37 1.87 Beading A A A B A A A B A Bleeding AA B B A A A B B Coating IJ IJ IJ IJ IJ IJ RC IJ IJ layer forming process(after 60 seconds) Gas 99% 99% 99% 99% 99% 99% 99% 99% 99% resistanceSticky feel A A A A A A A B A OD 2.09 2.28 2.31 2.43 2.01 1.98 2.05 2.461.92 Beading A A A B A A A B A Bleeding A A A A A A A A A

EXAMPLES 41 TO 49

[0441] (Preparation 1 of Liquid Composition)

[0442] {Liquid Composition 6A}

[0443] A styrene-acrylic acid copolymer 6A (St (styrene)/AA (acrylicacid)=70/30 (% by weight); molecular weight: 10,000; acid value: 201)synthesized by a solution polymerization process using a radicalinitiator was used to prepare Liquid Composition 6A of the followingcomposition. Incidentally, potassium hydroxide was used as a basicsubstance, and the amount added was controlled in such a manner that thepH of each liquid composition is 8.0. Styrene-acrylic acid copolymer 6A 3 parts Glycerol  7 parts Diethylene glycol  5 parts Water 85 parts.

[0444] {Liquid Compositions 6B and 6C}

[0445] Liquid Compositions 6B and 6C were prepared in the same manner asin Liquid Composition.6A except that the styrene-acrylic acid copolymerwas changed as shown in Table 12.

[0446] (Production of Recording Medium)

[0447] {Recording Medium 6A}

[0448] Disperal HP13 (trade name; product of CONDEA Co.) as an aluminahydrate was mixed with purified water to prepare a dispersion containing5% of solids. Hydrochloric acid was then added to the dispersion toadjust the pH of the dispersion to 4. After stirring the dispersion fora while, the dispersion was heated to 95° C. with stirring and kept for2 hours at the same temperature. The pH of the dispersion was adjustedto 9.5 with caustic soda, and the dispersion was then kept for 8 hourswith stirring. After 8 hours, the temperature of the dispersion wascooled down to room temperature, and the pH thereof was adjusted to 7.2.Thereafter, a desalting treatment was conducted, and acetic acid wasadded to conduct a deflocculating treatment, thereby obtaining colloidalsol. Alumina hydrate obtained by drying the colloidal sol of thisalumina hydrate was determined by X-ray diffractometry and found to havea pseudoboehmite structure. At this time, the BET specific surface areawas 150.2 m²/g, and the pore volume was 0.68 ml/g. Incidentally, thespecific surface area and pore volume were determined by the followingrespective methods.

[0449] 1) Pore volume (PV): determined by means of “AUTOSORB I” (tradename, manufactured by Quantachrome Co.) in accordance with the nitrogenadsorption and desorption method after a sample was subjected to adegassing treatment at 120° C. for 24 hours.

[0450] 2) BET specific surface area (SA): calculated out in accordancewith the method of Brunauer, et al.

[0451] Polyvinyl alcohol PVA117 (trade name, product of Kuraray Co.,Ltd.) was dissolved in purified water to obtain a 9% solution. Colloidalsol of the alumina hydrate obtained above was concentrated to obtain a17% solution. The colloidal sol of the alumina hydrate and the polyvinylalcohol solution were mixed with each other so as to give a weight ratioof 10:1 in terms of solids and stirred to obtain a dispersion.

[0452] After a 5% aqueous solution of sodium borate was applied on to abaryta layer of a base material having the baryta layer in advance by anair knife coater so as to give a coating weight of 10 g/m², theabove-prepared dispersion was further applied by a die coater so as togive a dry coating weight of 30 g/m². The base material used at thistime was obtained by applying a baryta composition composed of 100 partsof barium sulfate and 10 parts of gelatin on to a fibrous base having abasis weight of 150 g/m² and a Stöckigt sizing degree of 200 seconds soas to give a dry coating weight of 30 g/m² and calendaring it.

[0453] The surface of the ink-receiving layer provided on the basematerial having the baryta layer was subjected to a rewet castingtreatment with hot water (80° C.) by means of a rewet cast coater toobtain a glossy recording medium. Polyethylene was additionallylaminated by an extrusion laminator so as to give a coating weight of 20g/m². An aqueous solution of calcium chloride was applied on to thisrecording medium by a wire bar and dried to obtain Recording Medium 6Aadjusted to a polyvalent metal ion concentration of 0.01 (mol/L).

[0454] {Recording Media 6B to 6E}

[0455] Recording Media 6B to 6E were obtained in the same manner as inRecording Medium 6A except that calcium chloride (polyvalent metal salt)and polyvalent metal ion concentration in Recording Medium 6A werechanged as shown in Table 12.

[0456] (Examples 41 to 49)

[0457] The liquid compositions and the recording media were combined asshown in Table 12 to make the following evaluation. In each recordedarticle obtained, it was confirmed by observation of its section througha scanning electron microscope that a thin film having its correspondingthickness shown in Table 12 is formed. The results are shown in Table12.

EXAMPLES 50 TO 52

[0458] When the content of the styrene-acrylic acid copolymer in LiquidComposition 6A used in EXAMPLE 41 was changed to 6 parts (LiquidComposition 6D, EXAMPLE 50), 1.0 part (Liquid Composition 6E, EXAMPLE51) and 0.2 parts (Liquid Composition 6F, EXAMPLE 52), respectively, thethickness of the thin film layer was changed to 970 nm, 50 nm and 20 nm,respectively.

[0459] (Evaluation Method)

[0460] (Printing)

[0461] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (90% and100%) and secondary color printing (200%) with color inks of thefollowing respective compositions.

[0462] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Water  75 parts.

[0463] Dyes for Inks:

[0464] Y: C.I. Acid Yellow 23

[0465] M: C.I. Acid Red 52

[0466] C: C.I. Direct Blue 199

[0467] Bk: C.I. Food Black 2.

[0468] (Formation of Coating Layer; Ink-Jet Process)

[0469] After printing with the recording liquids respectively containingthe above-described coloring materials, solid printing (200%) with theliquid composition was conducted in the same manner as described aboveso as to completely cover the sites at which solid printing had beenconducted with the respective color inks.

[0470] (Formation of Coating Layer; Coating Process)

[0471] After printing with the recording liquids respectively containingthe above-described coloring materials, the liquid composition wasapplied in an amount of 20 g/m² by a roll coater so as to completelycover the sites at which solid printing had been conducted with therespective color inks.

[0472] (Gas Resistance)

[0473] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0474] (Tint)

[0475] The tint of the monochromatic solid print portions (90% and 100%)of cyan prepared above was visually evaluated in accordance with thefollowing standard. TABLE 12 EXAMPLE 41 EXAMPLE 42 EXAMPLE 43 EXAMPLE 44EXAMPLE 45 EXAMPLE 46 Liquid composition 6A 6C 6B 6A 6A 6A St/AA 70/3080/20 55/45 70/30 70/30 70/30 Molecular weight 10,000 9,000 12,00010,000 10,000 10,000 Recording medium 6B 6A 6C 6H 6D 6E Polyvalent metalCa(NO₃)₂ CaCl₂ CaCl₂ CaCl₂ Mg(NO₃)₂ Y(NO₃)₃ salt Polyvalent metal 4.00.5 100 50 4.0 4.0 ion concentration (mg/g) Process for Ink-jet Ink-jetInk-jet Ink-jet Ink-jet Ink-jet forming coating layer Thickness of 350220 510 450 390 410 coating layer (nm) Gas resistance (%) 98 97 92 98 9898 Tint A A B A A A EXAMPLE 47 EXAMPLE 48 EXAMPLE 49 EXAMPLE 50 EXAMPLE51 EXAMPLE 52 Liquid composition 6A 6A 6A 6D 6E 6F St/AA 70/30 70/3070/30 70/30 70/30 70/30 Molecular weight 10,000 10,000 10,000 10,00010,000 10,000 Recording medium 6F 6G 6B 6B 6B 6B Polyvalent metalZrO(CH₃OOO)₂ La(NO₃)₃ Ca(NO₃)₂ Ca(NO₃)₂ Ca(NO₃)₂ Ca(NO₃)₂ saltPolyvalent metal 4.0 4.0 4.0 4.0 4.0 4.0 ion concentration (mg/g)Process for Ink-jet Ink-jet Roll Ink-jet Ink-jet Ink-jet forming coatingcoating layer Thickness of 340 380 330 970 50 20 coating layer (nm) Gasresistance (%) 98 98 98 99 90 70 Tint A A A A A A

EXAMPLES 53 TO 57

[0476] (Preparation of Liquid Composition)

[0477] {Liquid Composition 7A}

[0478] A styrene-acrylic acid copolymer 7A (St/AA=80/20 (% by weight);molecular weight: 10,000; actual acid value: 132) synthesized by asolution polymerization process using a radical initiator was used toprepare Liquid Composition 7A of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and theamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. Styrene-acrylic acid copolymer 7A 3 parts Glycerol 7parts Diethylene glycol 5 parts Water 84 parts BC-30TX (polyoxyethylenecetyl 1 part. ether (EO 30), product of Nippon Surfactant Kogyo K.K.)

[0479] {Liquid Composition 7B}

[0480] Liquid Composition 7B was prepared in the same manner as inLiquid Composition 7A except that a benzyl acrylate-acrylic acidcopolymer 7B (BzA/AA=90/10 (% by weight); molecular weight: 11,000;actual acid value: 70) synthesized by a solution polymerization processusing a radical initiator was used in place of the styrene-acrylic acidcopolymer 7A.

[0481] {Liquid Composition 7C}

[0482] Liquid Composition 7C was prepared in the same manner as inLiquid Composition. 7A except that an n-butyl methacrylate-acrylic acidcopolymer 7C (nBMA/AA=80/20 (% by weight); molecular weight: 10,500;actual acid value: 130) synthesized by a solution polymerization processusing a radical initiator was used in place of the styrene-acrylic acidcopolymer 7A.

[0483] {Liquid Composition 7D}

[0484] The n-butyl methacrylate-acrylic acid copolymer 7C was used toprepare Liquid Composition 7D of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and theamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. copolymer 7C 3 parts Glycerol 7 parts Diethyleneglycol 5 parts Water 84.95 parts    BC-30TX (polyoxyethylene cetyl 0.05parts.  ether (EO 30), product of Nippon Surfactant Kogyo K.K.)

[0485] {Liquid Composition 7E}

[0486] The n-butyl methacrylate-acrylic acid copolymer 7C was used toprepare Liquid Composition 7E of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and anamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. n-Butyl methacrylate-acrylic acid 3 parts copolymer7C Glycerol 7 parts Diethylene glycol 5 parts Water 84 parts BC-5(polyoxyethylene cetyl 1 part. ether (EO 5), product of NipponSurfactant Kogyo K.K.)

[0487] (Recording Medium)

[0488] The Recording Medium 6B used in EXAMPLE 41 was used.

[0489] (Evaluation Method)

[0490] (Printing)

[0491] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (100%)with color inks of the following respective compositions, and solidprinting (200%) was then conducted with the liquid composition so as tocompletely cover the sites at which solid printing had been conductedwith the respective color inks.

[0492] Ink Composition: Dye (Y, M C or Bk) 4 parts Ethylene glycol 5parts Glycerol 10 parts  Ethyleneurea 5 parts Water  76 parts. 

[0493] Dyes for Inks:

[0494] Y: C.I. Direct Yellow 86

[0495] M: C.I. Acid Red 52

[0496] C: C.I. Direct Blue 199

[0497] Bk: C.I. Food Black 2.

[0498] (Gas Resistance)

[0499] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0500] (Ejection Stability)

[0501] An ink-jet recording head evaluation apparatus CANVAS (tradename, manufactured by Canon Inc.) and a printing head for Canon PrinterBJF-660 were used to judge a scatter of ejection velocity between therespective inks under the same conditions as head driving conditions forprinting by the printer.

[0502] A: At most 1 m/s;

[0503] B: 1 to 2 m/s;

[0504] C: 2 to 4 m/s;

[0505] D: At least 4 m/s.

EXAMPLES 53 TO 57

[0506] The above evaluation was made by combining the liquid compositionand the recording medium as shown in Table 13. TABLE 13 EXAMPLE 53EXAMPLE 54 EXAMPLE 55 EXAMPLE 56 EXAMPLE 57 Liquid Liquid Liquid LiquidLiquid Liquid composition Composition Composition CompositionComposition Composition 7A 7B 7C 7D 7E Recording Recording RecordingRecording Recording Recording medium Medium 6B Medium 6B Medium 6BMedium 6B Medium 6B Gas 98 99 86 81 82 resistance (%) Ejection A A A B Bstability

EXAMPLES 58 TO 64

[0507] (Preparation of Liquid Composition)

[0508] {Liquid Composition 8A}

[0509] An n-butyl acrylate-acrylic acid copolymer (nBA/AA=85/15 (% byweight); molecular weight: 10,000) and a styrene-acrylic acid copolymer(St/AA=70/30 (% by weight); molecular weight: 10,000) synthesized by asolution polymerization process using a radical initiator were used toprepare Liquid Composition 8A of the following composition.Incidentally, potassium hydroxide was used as a basic substance, and anamount added was controlled in such a manner that the pH of each liquidcomposition is 8.0. n-Butyl acrylate-acrylic acid 1.5 parts copolymerStyrene-acrylic acid copolymer 1.5 parts Glycerol   7 parts Diethyleneglycol   5 parts Water   85 parts.

[0510] (Recording Medium)

[0511] Recording Media 6A to 6C respectively used in EXAMPLEs 41 to 43were used.

[0512] (Examples 58 to 60)

[0513] The liquid compositions and the recording media were combined asshown in Table 15 to make the following evaluation. In each recordedarticle obtained, it was confirmed by observation of its section througha scanning electron microscope that a coating layer having itscorresponding thickness shown in Table 15 is formed. The results areshown in Table 15.

[0514] (Examples 61 and 62)

[0515] The content of the n-butyl acrylate-acrylic acid copolymer inLiquid Composition 8A was changed to 8 parts (Liquid Composition 8B) and0.5 parts (Liquid Composition 8C), respectively, to make the followingevaluation in combination with the respective recording media shown inTable 15. The results are shown in Table 15.

[0516] {Liquid Composition 8D}

[0517] Liquid Composition 8D was prepared in the same manner as inLiquid Composition 8A except that the n-butyl acrylate-acrylic acidcopolymer in Liquid Composition 8A was changed to a 2-ethylhexylacrylate-acrylic acid copolymer (2EHA/AA=85/15 (% by weight); molecularweight: 10,000).

[0518] Incidentally, preparation conditions for the respective liquidcompositions are shown in Table 14.

[0519] (Example 63)

[0520] The liquid composition and the recording medium were combined asshown in Table 15 to make the following evaluation. The results areshown in Table 15.

[0521] (Example 64)

[0522] After printing on Recording Medium 6B, Liquid Composition 8A wasapplied by a wire bar. At this time, it was confirmed that a coatinglayer having a thickness of 0.34 μm and an impregnated layer having athickness of 1.0 μm are formed on the surface and in the interior of thesurface layer, respectively. This recorded article was evaluated by thefollowing respective evaluation methods. As a result, the gas resistancewas 98%, and both rub-off resistance and tint were good (A).

[0523] (Evaluation Method)

[0524] (Printing)

[0525] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (90% and100%) and secondary color-printing (200%) with color inks of thefollowing respective compositions, and solid printing (200%) with theliquid composition was then conducted in the same manner as describedabove so as to completely cover the sites at which solid printing hadbeen conducted with the respective color inks.

[0526] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Water  75 parts.

[0527] Dyes for Inks:

[0528] Y: C.I. Acid Yellow 23

[0529] M: C.I. Acid Red 52

[0530] C: C.I. Direct Blue 199

[0531] Bk: C.I. Food Black 2.

[0532] (Gas Resistance)

[0533] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0534] (Rub-Off Resistance)

[0535] After the monochromatic solid print portion (100%) of blackprepared above was rubbed 5 times with silbon paper under a load of 40g/cm², the above-described test as to the gas resistance was conductedto visually evaluate it as to the rub-off resistance in accordance withthe following standard.

[0536] A: No scratch-like discoloration occurred at the rubbed portion;

[0537] B: Scratch-like discoloration was slightly observed at the rubbedportion, but it was not observed when viewed 30 cm away;

[0538] C: Scratch-like discoloration was observed at the rubbed portioneven when viewed 30 cm away.

[0539] (Tint)

[0540] The tint of the monochromatic solid print portions (90% and 100%)of cyan prepared above was visually evaluated in accordance with thefollowing standard.

[0541] A: The tint was not changed at the 100% cyan solid print portion;

[0542] B: The tint was not changed at the 90% cyan solid print portion;

[0543] C: The tint was somewhat reddish at the 90% cyan solid printportion. TABLE 14 Polymer 1 Polymer 2 Molecular Amount added MolecularAmount added Composition weight (parts) Composition weight (parts)Liquid nBA/AA = 10,000 1.5 St/AA = 10,000 1.5 Composition 85/15 70/30 8ALiquid nBA/AA = 10,000 8 St/AA = 10,000 1.5 Composition 85/15 70/30 8BLiquid nBA/AA = 10,000 0.5 St/AA = 10,000 1.5 Composition 85/15 70/30 8CLiquid 2EHA/AA = 9,000 1.5 St/AA = 10,000 1.5 Composition 85/15 70/30 8D

[0544] TABLE 15 Ex. 58 Ex. 59 Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 Liquidcomposition 8A 8A 8A 8B 8C 8D 8A Recording medium 6B 6A 6C 6B 6B 6B 6BThickness of 0.33 0.15 0.43 0.32 0.32 0.33 0.34 coating layer onrecording medium surface (μm) Thickness of 1 1.2 0.7 1.3 0.2 0.4 1coating layer within recording medium (μm) Gas resistance 98 98 98 99 9594 98 Rub-off resistance A A A A B A A Tint A A A A A A A

EXAMPLES 65 TO 70

[0545] <Recording Medium>

[0546] Recording Medium 6B used in EXAMPLE 41 was used.

[0547] <Preparation Example of Water-Soluble High-Molecular CopolymerRelated to Liquid Composition>

[0548] Preparation Example 9-1:

[0549] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 70.0 g ofbenzyl methacrylate and 30.0 g of methacrylic acid was separatelyprovided. In addition, a dropping funnel charged with 100 g of PGM and2.0 g of a polymerization initiator, tert-butyl peroxybenzoate wasseparately provided. The respective contents in these 2 dropping funnelswere added dropwise into the reactor over 2 hours. After completion ofthe addition, the reaction mixture was kept for 2 hours at a temperatureof from 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 29.1 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a colorless and transparent solution. The actualacid value and weight average molecular weight of the polymer were 172and 9,700, respectively.

[0550] Preparation Example 9-2:

[0551] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 80.0 g ofcyclohexyl acrylate and 20.0 g of acrylic acid was separately provided.In addition, a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 23.1 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a colorless and transparent solution. The actualacid value and weight average molecular weight of the polymer were 126and 7,100, respectively.

[0552] Preparation Example 9-3:

[0553] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to a reflux temperature while introducing nitrogengas and stirring them. A dropping funnel charged with 68.0 g of styreneand 32.0 g of acrylic acid was separately provided. In addition, adropping funnel charged with 100 g of PGM and 2.0 g of a polymerizationinitiator, tert-butyl peroxybenzoate was separately provided. Therespective contents in these 2 dropping funnels were added dropwise intothe reactor over 2 hours. After completion of the addition, the reactionmixture was kept for 2 hours at a temperature of from 70 to 80° C.Thereafter, the introduction of nitrogen gas was stopped, and thesolvent, PGM was removed outside the system by steam distillation, and18.5 g of 48% caustic soda and 200 g of ion-exchanged water were addedto conduct neutralization. The thus-obtained aqueous polymer solutionwas a pale yellow and transparent solution. The actual acid value andweight average molecular weight of the polymer were 205 and 7,900,respectively.

[0554] Preparation Example 9-4:

[0555] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 84.0 g ofbutyl methacrylate and 16.0 g of acrylic acid was separately provided.In addition, a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 37.0 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a pale yellow and transparent solution. The actualacid value and weight average molecular weight of the polymer were 115and 9,500, respectively.

[0556] Preparation Example 9-5:

[0557] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to a reflux temperature while introducing nitrogengas and stirring them. A dropping funnel charged with 65 g of styrene,15 g of n-butyl acrylate and 20 g of acrylic acid was separatelyprovided. In addition, a dropping funnel charged with 100 g of PGM and2.0 g of a polymerization initiator, tert-butyl peroxybenzoate wasseparately provided. The respective contents in these 2 dropping funnelswere added dropwise into the reactor over 2 hours. After completion ofthe addition, the reaction mixture was kept for 2 hours at a temperatureof from 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 23.1 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a pale yellow and transparent solution. The actualacid value and weight average molecular weight of the polymer were 145and 10,500, respectively.

[0558] Preparation Example 9-6:

[0559] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to a reflux temperature while introducing nitrogengas and stirring them. A dropping funnel charged with 85 g of n-butylacrylate and 15 g of acrylic acid was separately provided. In addition,a dropping funnel charged with 100 g of PGM and 2.0 g of apolymerization initiator, tert-butyl peroxybenzoate was separatelyprovided. The respective contents in these 2 dropping funnels were addeddropwise into the reactor over 2 hours. After completion of theaddition, the reaction mixture was kept for 2 hours at a temperature offrom 70 to 80° C. Thereafter, the introduction of nitrogen gas wasstopped, and the solvent, PGM was removed outside the system by steamdistillation, and 17.3 g of 48% caustic soda and 200 g of ion-exchangedwater were added to conduct neutralization. The thus-obtained aqueouspolymer solution was a pale yellow and transparent solution. The actualacid value and weight average molecular weight of the polymer were 108and 10,200, respectively.

[0560] <Preparation of Liquid Composition>

[0561] Liquid Composition 9A:

[0562] The water-soluble high-molecular copolymer obtained inPreparation Example 9-1 was mixed with glycerol, diethylene glycol,trimethylolpropane and ion-exchanged water at a mass ratio describedbelow, and the resultant mixture was stirred for 30 minutes. Thereafter,the mixture was filtered through a membrane filter having a pore size of0.2 μm to prepare Liquid Composition 9A.

[0563] Glycerol: 7%

[0564] Diethylene glycol: 5%

[0565] Trimethylolpropane: 7%

[0566] Water-soluble high-molecular copolymer obtained in PreparationExample 9-1: 3% (in terms of solids concentration of the polymer)

[0567] Ion-exchanged water: 78%.

[0568] The following Liquid Compositions 9B to 9F were prepared inaccordance with the preparation process of Liquid Composition 9A.

[0569] Liquid Composition 9B:

[0570] Glycerol: 7%

[0571] Diethylene glycol: 5%

[0572] Trimethylolpropane: 7%

[0573] Water-soluble high-molecular copolymer obtained in PreparationExample 9-2: 3% (in terms of solids concentration of the polymer)

[0574] Ion-exchanged water: 78%.

[0575] Liquid Composition 9C:

[0576] Glycerol: 7%

[0577] Diethylene glycol: 5%

[0578] Trimethylolpropane: 7%

[0579] Water-soluble high-molecular copolymer obtained in PreparationExample 9-3: 3% (in terms of solids concentration of the polymer)

[0580] Ion-exchanged water: 78%.

[0581] Liquid Composition 9D:

[0582] Glycerol: 7%

[0583] Diethylene glycol: 5%

[0584] Trimethylolpropane: 7%

[0585] Water-soluble high-molecular copolymer obtained in PreparationExample 9-4: 3% (in terms of solids concentration of the polymer)

[0586] Ion-exchanged water: 78%.

[0587] Liquid Composition 9E:

[0588] Glycerol: 7%

[0589] Diethylene glycol: 5%

[0590] Trimethylolpropane: 7%

[0591] Water-soluble high-molecular copolymer obtained in PreparationExample 9-5: 3% (in terms of solids concentration of the polymer)

[0592] Ion-exchanged water: 78%

[0593] Liquid Composition 9F:

[0594] Glycerol: 7%

[0595] Diethylene glycol: 5%

[0596] Trimethylolpropane: 7%

[0597] Water-soluble high-molecular copolymer obtained in PreparationExample 9-6: 3% (in terms of solids concentration of the polymer)

[0598] Ion-exchanged water: 78%.

[0599] Liquid Composition 9G:

[0600] Liquid Composition 9G was prepared in the same manner as inLiquid Composition 9A in accordance with the following composition.

[0601] Glycerol: 7%

[0602] Diethylene glycol: 5%

[0603] Trimethylolpropane: 7%

[0604] POVAL (polymerization degree 100): 3% (in terms of solidsconcentration of the polymer)

[0605] Ion-exchanged water: 78%.

[0606] (Examples 65 to 70 and Comparative Example 5)

[0607] Liquid Compositions 9A to 9G were evaluated according to thefollowing method. The results are shown in Table 16.

COMPARATIVE EXAMPLE 6

[0608] Recording Medium 6B was used as a blank as it is (withoutapplying any liquid composition).

[0609] (Evaluation Method)

[0610] (Printing)

[0611] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal energy to the ink in response torecording signals, was used to conduct momochromatic printing (100%) andsecondary color printing (200%) with color inks of the followingrespective compositions, and solid printing (200%) was then conductedwith the liquid composition so as to completely cover the sites at whichsolid printing had been conducted with the respective color inks.Further, solid printing (200%) with the liquid composition was alsoconducted on a non-printed portion.

[0612] Ink Composition: Dye (Y, M C or Bk) 4 parts Ethylene glycol 5parts Glycerol 10 parts  Ethyleneurea 5 parts Water  76 parts. 

[0613] Dyes for Inks:

[0614] Y: C.I. Direct Yellow 86

[0615] M: C.I. Acid Red 52

[0616] C: C.I. Direct Blue 199

[0617] Bk: C.I. Food Black 2.

[0618] (Gas Resistance)

[0619] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0620] TABLE 16 Liquid composition Gas resistance EXAMPLE 65 LiquidComposition 9A 99 EXAMPLE 66 Liquid Composition 9B 99 EXAMPLE 67 LiquidComposition 9C 98 EXAMPLE 68 Liquid Composition 9D 72 EXAMPLE 69 LiquidComposition 9E 95 EXAMPLE 70 Liquid Composition 9F 70 COMP. EXAMPLE 5Liquid Composition 9G 31 COMP. EXAMPLE 6 Blank 19

EXAMPLE 71 AND COMPARATIVE EXAMPLE 7

[0621] Liquid compositions containing the high-molecular copolymerobtained in Preparation Example 9-1 in amounts of 1.0 part, 3.0 parts,6.0 parts and 15.0 parts respectively were prepared in accordance withthe following respective compositions (EXAMPLE 71).

[0622] The liquid composition containing the high-molecular copolymerobtained in Preparation Example 9-1 in an amount of 1.0 part wasprepared in accordance with the following composition.

[0623] Glycerol: 7%

[0624] Diethylene glycol: 5%

[0625] Trimethylolpropane: 7%

[0626] Water-soluble high-molecular copolymer obtained in PreparationExample 9-1: 1% (in terms of solids concentration of the polymer)

[0627] Ion-exchanged water: 80%.

[0628] The liquid composition containing the high-molecular copolymerobtained in Preparation Example 9-1 in an amount of 6.0 parts wasprepared in accordance with the following composition.

[0629] Glycerol: 7%

[0630] Diethylene glycol: 5%

[0631] Trimethylolpropane: 7%

[0632] Water-soluble high-molecular copolymer obtained in PreparationExample 9-1: 6% (in terms of solids concentration of the polymer)

[0633] Ion-exchanged water: 75%.

[0634] The liquid composition containing the high-molecular copolymerobtained in Preparation Example 9-1 in an amount of 15.0 parts wasprepared in accordance with the following composition.

[0635] Glycerol: 7%

[0636] Diethylene glycol: 5%

[0637] Trimethylolpropane: 7%

[0638] Water-soluble high-molecular copolymer obtained in PreparationExample 9-1: 15% (in terms of solids concentration of the polymer)

[0639] Ion-exchanged water: 66%.

[0640] Liquid compositions (COMPARATIVE EXAMPLE 7) containing polyvinylalcohol (polymerization degree: 100) were prepared in the same manner asin EXAMPLE 71.

[0641] The respective liquid compositions and Recording Medium 6B werecombined to conduct the above-described evaluation. The results areshown in Table 17. TABLE 17 Concentration of Kind of high-high-molecular molecular copolymer copolymer (parts) Gas resistanceEXAMPLE 71 High-molecular 1.0 98 copolymer 3.0 99 obtained in 6.0 99Preparation 15.0 99 Example 9-1 COMPARATIVE Polyvinyl 1.0 28 EXAMPLE 7alcohol 3.0 31 (polymerization 6.0 32 degree: 100) 15.0 31

EXAMPLES 72 TO 75

[0642] <Recording Medium>

[0643] Recording Medium 6B used in EXAMPLE 41 was used. <PreparationExample of water-soluble high-molecular copolymer related to liquidcomposition>

[0644] Preparation Example 10-1:

[0645] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 69.0 g ofstyrene, 30.0 g of methacrylic acid and 1.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a colorless and transparentsolution.

[0646] Preparation Example 10-2:

[0647] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to a reflux temperature while introducing nitrogengas and stirring them. A dropping funnel charged with 65.0 g of styrene,30.0 g of methacrylic acid and 5.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a colorless and transparentsolution.

[0648] Preparation Example 10-3:

[0649] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to a reflux temperature while introducing nitrogengas and stirring them. A dropping funnel charged with 60.0 g of styrene,30.0 g of methacrylic acid and 10.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a pale yellow and transparentsolution.

[0650] Preparation Example 10-4:

[0651] A reactor equipped with a stirrer and a reflux condenser wascharged with 150 g of PGM that is a polymerization solvent, and thecontents were heated to the reflux temperature while introducingnitrogen gas and stirring them. A dropping funnel charged with 50.0 g ofstyrene, 30.0 g of methacrylic acid and 20.0 g of2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole wasseparately provided. In addition, a dropping funnel charged with 100 gof PGM and 2.0 g of a polymerization initiator, tert-butylperoxybenzoate was separately provided. The respective contents in these2 dropping funnels were added dropwise into the reactor over 2 hours.After completion of the addition, the reaction mixture was kept for 2hours at a temperature of from 70 to 80° C. Thereafter, the introductionof nitrogen gas was stopped, and the solvent, PGM was removed outsidethe system by steam distillation, and 29.1 g of 48% caustic soda and 200g of ion-exchanged water were added to conduct neutralization. Thethus-obtained aqueous polymer solution was a pale yellow and transparentsolution.

[0652] <Preparation of Liquid Composition>

[0653] Liquid Composition 10A:

[0654] The water-soluble high-molecular copolymer obtained inPreparation Example 10-1 was mixed with glycerol, diethylene glycol,trimethylolpropane and ion-exchanged water at a mass ratio describedbelow, and the resultant mixture was stirred for 30 minutes. Thereafter,the mixture was filtered through a membrane filter having a pore size of0.2 μm to prepare Liquid Composition 10A.

[0655] Glycerol: 7%

[0656] Diethylene glycol: 5%

[0657] Trimethylolpropane: 7%

[0658] Water-soluble high-molecular copolymer obtained in PreparationExample 10-1: 3% (in terms of solids concentration of the polymer)

[0659] Ion-exchanged water: 78%.

EXAMPLE 72

[0660] An ink-jet printer (BJF870, trade name, manufactured by CanonInc.) was used to conduct momochromatic printing (100%) on RecordingMedium 6B used in EXAMPLE 41 with color inks of the following respectivecompositions, and solid printing (200%) with Liquid Composition 10A wasthen conducted so as to completely cover the sites at which solidprinting had been conducted with the respective color inks. Thethus-obtained recorded article was evaluated as to gas resistance andlight fastness in accordance with the following respective methods.Further, UV absorption spectrophotometry was also conducted.

[0661] (Gas Resistance)

[0662] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%) (Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0663] (Light Fastness)

[0664] The monochromatic solid print portion (100%) of magenta preparedabove was subjected to an exposure test as to light fastness by means ofa fluorescent lamp light fastness tester under the following conditions.The light fastness was evaluated in terms of a rate (%) of change of theimage density after the light fastness test.

Light fastness (%)=(Image density after the fluorescent lamp test/Imagedensity before the fluorescent lamp test)×100 (%)

[0665] Test Conditions:

[0666] Light quantity irradiated: 70 klx

[0667] Test time: 520 hours

[0668] Temperature and humidity within test chamber: 24° C., 60% RH

[0669] Filter: soda lime.

[0670] (UV Absorption Spectrophotometry)

[0671] Liquid Composition 10A prepared above was applied on to a PETfilm to form a thin film, and a UV absorption spectrum (U-3300,manufactured by Hitachi Ltd.) was measured by using the PET film as ablank. As a result, the maximum absorption wavelength was 338.5 nm, andthe absorbance was 0.15. Further, as a result of observation throughSEM, the film thickness was found to be 0.48 μm, so that an absorptivitycoefficient “e” calculated out therefrom was 0.31.

[0672] (Preparation of Liquid Compositions 10B to 10D)

[0673] Liquid Compositions 10B to 10D were prepared in the same manneras in Liquid Composition 10A in accordance with the following respectivecompositions.

[0674] Liquid Composition 10B:

[0675] Glycerol: 7%

[0676] Diethylene glycol,: 5%

[0677] Trimethylolpropane: 7%

[0678] Water-soluble high-molecular copolymer obtained in PreparationExample 10-2: 3% (in terms of solids concentration of the polymer)

[0679] Ion-exchanged water: 78%.

[0680] Liquid Composition 10C:

[0681] Glycerol: 7%

[0682] Diethylene glycol: 5%

[0683] Trimethylolptopane: 7%

[0684] Water-soluble high-molecular copolymer obtained in PreparationExample 10-3: 3% (in terms of solids concentration of the polymer)

[0685] Ion-exchanged water: 78%.

[0686] Liquid Composition 10D:

[0687] Glycerol: 7%

[0688] Diethylene glycol: 5%

[0689] Trimethylolpropane: 7%

[0690] Water-soluble high-molecular copolymer obtained in PreparationExample 10-4: 3% (in terms of solids concentration of the polymer)

[0691] Ion-exchanged water: 78%.

[0692] (Examples 73 to 75)

[0693] EXAMPLEs 73 to 75 were performed in the same manner as in EXAMPLE72 except that Liquid Composition 10A in EXAMPLE 72 was changed as shownin Table 18.

COMPARATIVE EXAMPLE 8

[0694] Evaluation was conducted in the same manner as in EXAMPLE 72except that Liquid Composition 10A was not applied.

[0695] Evaluation results as to the gas resistance and light fastness inEXAMPLEs 72 to 75 are shown together with the results of COMPARATIVEEXAMPLE 8 in Table 18. TABLE 18 Light Example Liquid composition Gasresistance fastness EXAMPLE 72 Liquid Composition 10A 98 76 EXAMPLE 73Liquid Composition 10B 98 79 EXAMPLE 74 Liquid Composition 10C 98 80EXAMPLE 75 Liquid Composition 10D 98 81 COMPARATIVE Blank 19 73.5EXAMPLE 8

[0696] As apparent from Table 18, the liquid compositions respectivelycontaining the high-molecular copolymers obtained in PreparationExamples 10-1 to 10-4 were applied, whereby excellent light fastness wasachieved.

[0697] The results that each liquid composition was applied on to thePET film to form a thin film, and a UV absorption spectrum was measuredto calculate out the maximum absorption wavelength and the absorptivitycoefficient are shown in Table 19. TABLE 19 λ_(max) Absorptivitycoefficient EXAMPLE 72 338.5 0.31 EXAMPLE 73 338.5 1.56 EXAMPLE 74 338.53.01 EXAMPLE 75 338.5 5.98 COMP. EXAMPLE 8 No absorption appeared at 400nm or shorter

EXAMPLES 76 TO 84

[0698] (Preparation of Liquid Composition)

[0699] (Liquid Composition 11A)

[0700] A styrene-acrylic acid copolymer 11A (St/AA=70/30 (% by weight);molecular weight: 10,500; acid value: 206) synthesized by a solutionpolymerization process using a radical initiator was used to prepareLiquid Composition 11A of the following composition. Incidentally,potassium hydroxide was used as a basic substance, and an amount addedwas controlled in such a manner that the pH of each liquid compositionis 8.0. Styrene-acrylic acid copolymer 11A  3 parts Glycerol  7 partsDiethylene glycol  5 parts Water 85 parts.

[0701] (Liquid Compositions 11B and 11C)

[0702] Liquid Compositions 11B and 11C were prepared in the same manneras in Liquid Composition 11A except that the styrene-acrylic acidcopolymer was changed as shown in Table 21.

[0703] (Production of Recording Medium)

[0704] {Recording Medium 11A}

[0705] Aluminum sec-butoxide was prepared in accordance with the processdescribed in U.S. Pat. No. 4,242,271. A 75% mixed solution of thisaluminum sec-butoxide in sec-butyl alcohol was hydrolyzed at 85° C. witha mixed solution of sec-butyl alcohol containing 30% of water to obtainan alumina slurry. After the alumina slurry was aged at 125° C. for 3hours in an electromagnetically stirring autoclave, water wasimmediately added to the alumina slurry until a solids content was 20%,and the thus-treated alumina slurry was cooled. The pH of the aluminaslurry was adjusted with a 3.8% aqueous solution of nitric acid toobtain Alumina Hydrate 6A. Alumina hydrate A obtained by dryingcolloidal sol of this alumina hydrate was determined by X-raydiffractometry and found to have a pseudoboehmite structure. At thistime, the BET specific surface area was 175 m²/g, and the pore volumewas 0.65 ml/g. Incidentally, the specific surface area and pore volumewere determined by the following respective methods.

[0706] 1) Pore volume (PV): determined by means of “AUTOSORB I” (tradename, manufactured by Quantachrome Co.) in accordance with the nitrogenadsorption and desorption method after a sample was subjected to adegassing treatment at 120° C. for 24 hours.

[0707] 2) BET specific surface area (SA): calculated out in accordancewith the method of Brunauer, et al.

[0708] Polyvinyl alcohol PVA117 (trade name, product of Kuraray Co.,Ltd.) was dissolved in purified water to obtain a 9% solution. Colloidalsol of the alumina hydrate A was concentrated to obtain a 17% solution.The colloidal sol of the alumina hydrate A and the polyvinyl alcoholsolution were mixed with each other so as to give a weight ratio of 10:1in terms of solids and stirred to obtain a dispersion.

[0709] After a 5% aqueous solution of sodium borate was applied on to abaryta layer of a base material having the baryta layer in advance by anair knife coater so as to give a coating weight of 10 g/m², theabove-prepared dispersion was further applied by a die coater so as togive a dry coating weight of 30 g/m². The base material used at thistime was obtained by applying a baryta composition composed of 100 partsof barium sulfate and 10 parts of gelatin on to a fibrous base having abasis weight of 150 g/m² and a Stöckigt sizing degree of 200 seconds soas to give a dry coating weight of 30 g/m² and calendaring it.

[0710] The surface of the ink-receiving layer provided on the basematerial having the baryta layer was subjected to a rewet castingtreatment with hot water (80° C.) by means of a rewet cast coater toobtain a glossy recording medium. Polyethylene was additionallylaminated on a back side of the base material by an extrusion laminatorso as to give a coating weight of 20 g/m².

[0711] A 4% aqueous solution of calcium chloride was applied on to therecording medium prepared in the above-described manner by a wire barand dried to obtain Recording Medium 11A adjusted to a polyvalent metalion concentration of 0.15 mol/L.

[0712] {Recording Media 11B to 11D}

[0713] Recording Media 11B to 11D were obtained in the same manner as inRecording Medium 11A except that alumina hydrates 11B to 11D obtained bychanging the temperature and aging time in the synthesis of the aluminahydrate used in Recording Medium 11A as shown in Table 10 wererespectively used.

[0714] (Preparation of Recording Liquid Containing Coloring Material)

[0715] {Recording Liquid 11A}

[0716] Recording Liquid 11A of the following composition was prepared.

[0717] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Water 75 parts.

[0718] Dyes for Inks:

[0719] Y: C.I. Acid Yellow 23

[0720] M: C.I. Acid Red 52

[0721] C: C.I. Direct Blue 199

[0722] Bk: C.I. Food Black 2.

[0723] {Recording Liquid 11B}

[0724] Recording Liquid 11B of the following composition was prepared.

[0725] Ink Composition: Dye (Y, M C or Bk)  5 parts Ethylene glycol 10parts Polyethylene glycol 10 parts Acetylenol EH (product of Kawaken  2parts Fine Chemicals Co., Ltd.) Water 73 parts.

[0726] Dyes for Inks:

[0727] Y: C.I. Acid Yellow 23

[0728] M: C.I. Acid Red 52

[0729] C: C.I. Direct Blue 199

[0730] Bk: C.I. Food Black 2.

[0731] (Examples 76 to 84)

[0732] The liquid compositions, recording liquids, recording media andcoating layer forming process were combined as shown in Tables 20, 21and 22 to conduct the following evaluation.

[0733] (Evaluation Method)

[0734] (Printing)

[0735] An ink-jet recording apparatus (BJF660, trade name, manufacturedby Canon Inc.) having an On-Demand type multi-recording head, whichejects an ink by applying thermal-energy to the ink in response torecording signals, was used to conduct momochromatic printing (100%) andsecondary color printing (200%) with color inks of the above-describedrespective compositions.

[0736] (Formation of Coating Layer; Ink-Jet Process)

[0737] Upon elapsed time of 5 seconds and 60 seconds after printing withthe recording liquids respectively containing the above-describedcoloring materials, solid printing (200%) with the liquid compositionwas conducted in the same manner as described above so as to completelycover the sites at which solid printing had been conducted with therespective color inks.

[0738] (Formation of Coating Layer; Coating Process)

[0739] Upon elapsed time of 5 seconds and 60 seconds after printing withthe recording liquids respectively containing the above-describedcoloring materials, the liquid composition was applied in an amount of20 g/m² by a roll coater so as to completely cover the sites at whichsolid printing had been conducted with the respective color inks.

[0740] (Gas Resistance)

[0741] The monochromatic solid print portion (100%) of black preparedabove was placed in an ozone exposure tester (manufactured by SUGA TESTINSTRUMENTS CO., LTD.) and exposed to ozone at a concentration of 3 ppmfor 6 hours under conditions of 23° C. and 60% RH to evaluate the printas to gas resistance in terms of a rate (%) of change of the imagedensity after the ozone exposure test.

Gas resistance (%)=(Image density after the ozone exposure test/Imagedensity before the ozone exposure test)×100 (%)

[0742] (Stickiness of Coating Layer)

[0743] A sticky feel of each image-recorded article after formation ofthe coating layer produced above was evaluated in accordance with thefollowing standard.

[0744] A: No sticky feel existed after 20 seconds from formation of thecoating layer;

[0745] B: A sticky feel somewhat existed after 20 seconds from formationof the coating layer, but disappeared after 60 seconds;

[0746] C: A sticky feel existed even after 60 seconds from formation ofthe coating layer.

[0747] (Coloring Ability)

[0748] OD (optical density) of the monochromatic solid print portion(100%) of black in each image-recorded article after formation of thecoating layer produced above was measured (by 310TR manufactured byX-Rite Co.).

[0749] (Bleeding)

[0750] Bleeding at an edge portion of each solid printed image formedabove was visually evaluated in accordance with the following standard.

[0751] A: No bleeding occurred in the secondary solid printing (200%);

[0752] B: No bleeding occurred in the monochromatic solid printing(100%);

[0753] C: Bleeding occurred in the monochromatic solid printing (100%).

[0754] (Beading)

[0755] Beading of each solid printed image formed above was visuallyevaluated in accordance with the following standard.

[0756] A: No beading occurred in the secondary solid printing (200%);

[0757] B: No beading occurred in the monochromatic solid printing(100%);

[0758] C: Beading occurred in the monochromatic solid printing (100%).TABLE 20 Liquid composition 11A 11B 11C St/AA 70/30 62/38 55/45 Acidvalue 206 252 297 Molecular weight 10,500 9,000 13,000

[0759] TABLE 21 Recording medium 11A 11B 11C 11D Alumina hydrate 11A 11B11C 11D BET specific 175 198 212 130 surface area (m²/g) Pore volume(ml/g) 0.65 0.57 0.52 0.72

[0760] TABLE 22 Example Ex. 76 Ex. 77 Ex. 78 Ex. 79 Ex. 80 Ex. 81 Ex. 82Ex. 83 Ex. 84 Liquid 11A 11B 11B 11B 11B 11C 11A 11A 11C compositionRecording 11A 11A 11B 11A 11A 11B 11A 11A 11A liquid Recording 11A 11B11B 11C 11D 11B 11A 11C 11B medium Kα1 0.9 0.9 1 0.5 1.5 0.8 0.9 0.3 1.8Kα2 2.5 1.5 1 0.6 3 1 2.5 0.6 1.5 Kα1/Kα2 0.36 0.60 1.00 0.83 0.50 0.800.36 0.50 1.20 Coating IJ IJ IJ IJ IJ IJ RC IJ IJ layer forming process(after 5 seconds) Gas 99% 99% 99% 99% 99% 99% 99% 99% 99% resistanceSticky feel A A A A A A A B A OD 2.09 2.21 1.88 2.19 1.98 2.01 2.09 2.381.69 Beading A A A B A A A B A Bleeding A A B B A A A B B Coating IJ IJIJ IJ IJ IJ RC IJ IJ layer forming process (after 60 seconds) Gas 99%99% 99% 99% 99% 99% 99% 99% 99% resistance Sticky feel A A A A A A A B AOD 2.10 2.19 2.26 2.39 2.02 2.03 2.14 2.46 1.77 Beading A A A B A A A BA Bleeding A A A A A A A A A

[0761] According to the present invention, as described above, there canbe provided a process for forming an image-recorded article excellent ingas resistance and rub-off resistance without causing clogging at anorifice at high speed by a miniaturized apparatus.

What is claimed is:
 1. An image forming process for forming animage-recorded article having a coating layer on at least a part of animage formed, which comprises the steps of providing a liquidcomposition containing a polymer, providing an image-recorded articleformed on a recording medium by an ink-jet recording method, andapplying the liquid composition to at least a part of an image of therecorded article to insolubilize the polymer contained in the liquidcomposition on the surface of the image, thereby forming the coatinglayer at a position to which the liquid composition has been applied,wherein the recording medium has a surface which insolubilizes thepolymer.
 2. The image forming process according to claim 1, wherein thepolymer has a structure represented by —COOA (1), wherein A is an alkalimetal, ammonium or an organic ammonium, and the surface pH of therecording medium is a pH which insolubilizes the polymer.
 3. The imageforming process according to claim 1, wherein the polymer has astructure represented by —COOA (1), wherein A is an alkali metal,ammonium or an organic ammonium, and the recording medium contains apolyvalent metal ion which insolubilizes the polymer.
 4. The imageforming process according to any one of claims 1 to 3, wherein thepolymer is a vinyl copolymer containing a unit composed of an acrylicmonomer.
 5. The image forming process according to any one of claims 1to 3, wherein the polymer contains a unit composed of a monomer havingultraviolet absorbency.
 6. The image forming process according to anyone of claims 1 to 3, wherein the liquid composition contains asurfactant having ethylene oxide.
 7. The image forming process accordingto claim 2, wherein the recording medium has a porous ink-receivinglayer, and the surface pH thereof is within a range of from 5.4 to 7.0.8. The image forming process according to claim 7, wherein the recordingmedium has a porous ink-receiving layer containing an alumina hydrate.9. The image forming process according to claim 3, wherein the recordingmedium has a porous ink-receiving layer, and the ink-receiving layercontains any ion selected from the group consisting of an alkaline earthmetal ion, a rare earth metal ion and a zirconium ion.
 10. The imageforming process according to any one of claims 1 to 3, wherein anabsorption coefficient, K_(α) 1 from 0.025 seconds to 0.1 seconds in theBristow method of the liquid composition into the recording medium iswithin a range of from 0.5 to 1.5 (ml·m⁻²·msec^(−1/2)).
 11. The imageforming process according to any one of claims 1 to 3, wherein theliquid composition contains at least two water-soluble polymers.
 12. Animage forming process for forming an image-recorded article having acoating layer on an image formed, which comprises the steps of providinga liquid composition containing an aqueous medium and, a polymer havinga structure represented by a general formula —COOA   (1) wherein A is analkali metal, ammonium or an organic ammonium, providing animage-recorded article formed on a recording medium having a surface pHwhich insolubilizes the polymer by an ink-jet recording method, andapplying the liquid composition to the image-recorded article to formthe coating layer on the image-recorded article.
 13. The image formingprocess according to claim 12, wherein the recording medium has a porousink-receiving layer, and the surface pH of the ink-receiving layer iswithin a range of from 5.4 to 7.0.
 14. An image forming process forforming an image-recorded article having a coating layer on an imageformed, which comprises the steps of providing a liquid compositioncontaining an aqueous medium and a polymer having a structurerepresented by a general formula —COOA   (1) wherein A is an alkalimetal, ammonium or an organic ammonium, providing an image-recordedarticle formed on a recording medium containing a polyvalent metal ionwhich insolubilizes the polymer by an ink-jet recording method, andapplying the liquid composition to the image-recorded article to formthe coating layer on the image-recorded article.
 15. The image formingprocess according to claim 14, wherein the recording medium has a porousink-receiving layer, and the ink-receiving layer contains a polyvalentmetal ion.
 16. A liquid composition for forming a coating layer on atleast a part of an image-recorded article formed on a recording mediumby an ink-jet recording method, which comprises an aqueous medium and apolymer having a structure represented by a general formula —COOA   (1)wherein A is an alkali metal, ammonium or an organic ammonium, whereinthe polymer is dissolved in the aqueous medium in such a state as to beinsolubilized by the surface pH of the recording medium.
 17. A liquidcomposition for forming a coating layer on at least a part of animage-recorded article formed on a recording medium by an ink-jetrecording method, which comprises an aqueous medium and a polymer havinga structure represented by a general formula —COOA   (1) wherein A is analkali metal, ammonium or an organic ammonium, wherein the polymer isdissolved in the aqueous medium in such a state as to be insolubilizedby a polyvalent metal ion contained in the recording medium.
 18. Anink-jet recording apparatus comprising a liquid holding part for holdinga liquid therein and a liquid ejecting part for ejecting the liquid fedfrom the liquid holding part, wherein the liquid is the liquidcomposition according to claim 16 or
 17. 19. An image-recorded articleobtained by the image forming process according to any one of claims 1,12 and
 14. 20. The image-recorded article according to claim 19, whereinthe coating layer formed on the image further comprises a layercontaining a polymer impregnated into the surface layer of the image andinsolubilized.